Composition, nonlinear optical element, optical modulator, and polymer compound

Abstract

The present invention addresses the problem of providing: a composition and a polymer compound which are each capable of suppressing aggregation of a dye that has a nonlinear optical effect in a nonlinear optical material, and exhibiting a higher electro-optic effect with respect to the absorbance after poling; a nonlinear optical element which is obtained using the composition; and an optical modulator which comprises the nonlinear optical element and operates on the basis of an electro-optic effect. The present invention pertains to a composition which contains a compound represented by formula (1) and a compound represented by formula (3), wherein the content of the compound represented by formula (3) is 0.0001 mol% to 25 mol% inclusive relative to the total content of the compound represented by formula (1) and the compound represented by formula (3).　(Definitions of groups are as set forth in the description.)

Description

Composition, nonlinear optical element, optical modulator, and polymer compound

[0001] The present invention relates to a composition, a nonlinear optical element, an optical modulator, and a polymer compound.

[0002] In recent years, development of various optoelectronic devices using nonlinear optical materials has been progressing in fields such as optical information processing and optical communications. Nonlinear optical materials are materials that exhibit a polarization response proportional to the square, cube, or higher order terms of the magnitude of the electric field of light, and those that produce the first-order electro-optic effect (Pockels effect), which is a second-order nonlinear optical effect, are being considered for applications such as optical switches and optical modulation.

[0003] Nonlinear optical materials, particularly organic nonlinear optical materials, are generally obtained by blending or bonding a compound (dye) having nonlinear optical activity with a polymeric material such as polymethyl methacrylate (PMMA). The nonlinear optical properties are expressed by the electro-optic coefficient (hereinafter also referred to as the "EO coefficient"), also expressed as r33. Known dyes include so-called push-pull π-conjugated compounds having an electron-donating group and an electron-withdrawing group at each end of the molecular structure, and a π-conjugated chain connecting these. Nonlinear optical materials are desired to have a high electro-optic coefficient, high heat resistance, and low absorption loss at wavelengths used in optical communications.

[0004] The electro-optic effect is induced by orienting a nonlinear optical material in a state lacking a center of inversion symmetry. Therefore, when using organic nonlinear optical materials in nonlinear optical elements, it is necessary to maintain the dye in a certain orientation state. To achieve this orientation state, a poling process (poling treatment) must be performed on the organic nonlinear optical material at a temperature near the glass transition temperature of the polymeric material (Patent Documents 1 to 4). However, because dyes with nonlinear optical activity have a large dipole moment, strong intermolecular interactions occur, promoting association between the dyes. This reduces the poling effect, preventing a high electro-optic effect from being achieved, and research and development is being conducted to address this issue.

[0005] For example, Patent Document 5 describes that by using a polymer material having electron-withdrawing substituents in the molecule and a composition of an organic compound exhibiting a nonlinear optical effect as a nonlinear optical material, the rate of change in absorbance before and after poling treatment increases (indicating a large poling effect). On the other hand, since changes in the electronic state of the entire polymer due to the strong electron-withdrawing group affect the association state of the polymer, there is concern that the poling effect may be insufficient depending on the doping amount of the electron-withdrawing group and the type of polymer.

[0006] Furthermore, Non-Patent Document 1 describes that a composition obtained by mixing a polymer compound exhibiting a nonlinear optical effect, in which a dye (host dye) with a short π-conjugated chain is bound to a polymer material (hereinafter also referred to as an "EO polymer"), with a dye (guest dye) exhibiting a nonlinear optical effect in a 1:1 ratio, exhibits a high nonlinear optical effect after poling. In order to maximize the effect of this technique, it is necessary to mix the host dye with the guest dye exhibiting a high nonlinear optical effect in a 1:1 ratio, which poses a problem in that the amount of guest dye doped in the nonlinear optical material is limited.

[0007] International Publication No. 2019 / 151318 Japanese Patent Application Laid-Open No. 2010-066325 International Publication No. 2011 / 024774 Japanese Patent Application Laid-Open No. 2015-178544 Japanese Patent Application Laid-Open No. 2023-152032

[0008] RSC Adv. ,2016,6,1618-1626

[0009] An object of the present invention is to provide a composition and a polymer compound that can suppress the aggregation of dyes having a nonlinear optical effect in a nonlinear optical material and that exhibit a higher electro-optic effect relative to absorbance after poling. Another object of the present invention is to provide a nonlinear optical element using the composition, and an optical modulator that includes the nonlinear optical element and operates based on the electro-optic effect.

[0010] As a result of extensive research in light of the above-mentioned problems, the present inventors have found that compositions containing dye compounds exhibiting nonlinear optical effects and compounds having specific structures similar thereto exhibit lower absorption loss and a high electro-optic effect after poling treatment, i.e., exhibit a high electro-optic effect relative to absorbance, and have completed the present invention.

[0011] The gist of the present invention is as follows.

[0012] A first aspect of the present invention relates to a composition comprising a compound represented by the following formula (1) and a compound represented by the following formula (3), wherein the content of the compound represented by the following formula (3) is 0.0001 mol % or more and 25 mol % or less with respect to the total content of the compound represented by the following formula (1) and the compound represented by the following formula (3):

[0013]

[0014] [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15.

[0015]

[0016] [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent.

[0017]

[0018] [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2).３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

[0019] Aspect 2 of the present invention is the composition of aspect 1, wherein in the formula (3), Z ３１ is a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a cyano group, an aldehyde group, or a carboxy group.

[0020] Aspect 3 of the present invention is the composition of aspect 1 or 2, wherein Y in formula (1) １１ are each independently represented by the following formula (4), and Y in the formula (3) ３１ are each independently represented by the following formula (5), provided that n １１ When R is 2 or more, R in the following formula (4) ４１ and R ４２ is another Y １１ R included in ４１ or R ４２ may be linked to form a ring, and n in the formula (3) ３１ When R is 2 or more, R in the following formula (5) ５１ and R ５２ is another Y ３１ R included in ５１ or R ５２ and optionally linked to form a ring.

[0021]

[0022] [In formula (4), R ４１ and R ４２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ４１ and R ４２ may be bonded to form a ring.

[0023]

[0024] [In formula (5), R ５１ and R ５２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ５１ and R ５２ may be bonded to form a ring.

[0025] A fourth aspect of the present invention is a composition according to any one of the first to third aspects, wherein Y in the formula (1) １１ and Y in the formula (3) ３１ are each independently represented by the following formula (6), the following formula (7), or the following formula (8), provided that n １１ When R is 2 or more, R in the following formula (6), the following formula (7), or the following formula (8) ６１ and R ６２ , R７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y １１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ may be linked to form a ring, and n in the formula (3) ３１ When R is 2 or more, R in the following formula (6), the following formula (7), or the following formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y ３１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ and optionally linked to form a ring.

[0026]

[0027] [In formula (6), R ６１ and R ６２are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ６１ and R ６２ may be bonded to form a ring.

[0028]

[0029] [In formula (7), R ７１ and R ７２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ７１ and R ７２ may be bonded to form a ring, ７１ is O, S or N-Q ７１ and Q ７１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent.

[0030]

[0031] [In formula (8), R ８１ ~R ８７are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ８１ ~R ８７ At least two of these may be bonded to form a ring.

[0032] Aspect 5 of the present invention is a composition according to any one of aspects 1 to 4, wherein n in formula (1) １１ is n in the formula (3). ３１ The composition is one or more times greater than

[0033] A sixth aspect of the present invention is a composition according to any one of the first to fifth aspects, wherein Z in the formula (1) １１ and Z in the formula (3) ３１ and R in the formula (1) １４ and R in the formula (3) ３４ The present invention relates to a composition in which the structure of the compound represented by formula (1) is the same as the structure of the compound represented by formula (3), except for the following:

[0034] A seventh aspect of the present invention relates to the composition of any one of the first to sixth aspects, further comprising a polymeric material.

[0035] Aspect 8 of the present invention relates to the composition of Aspect 7, wherein the polymer material is at least one selected from the group consisting of polymethyl(meth)acrylate, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, and copolymers thereof.

[0036] A ninth aspect of the present invention relates to the composition of any one of the first to eighth aspects, further comprising an organic solvent.

[0037] A tenth aspect of the present invention relates to a composition comprising a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1), and a compound represented by the following formula (3):

[0038]

[0039] [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15.

[0040]

[0041] [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent.

[0042]

[0043] [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

[0044] An eleventh aspect of the present invention relates to a composition comprising a compound represented by the following formula (1) and a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3):

[0045]

[0046] [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15.

[0047]

[0048] [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent.

[0049]

[0050] [In formula (3), Ar ３１are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

[0051] A twelfth aspect of the present invention relates to a composition comprising: a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1); and a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3):

[0052]

[0053] [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15.

[0054]

[0055] [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent.

[0056]

[0057] [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

[0058] A thirteenth aspect of the present invention relates to a composition comprising a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1) and a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3), wherein the content of the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3) in the nonlinear optically active polymer compound is 0.0001 mol % or more and 25 mol % or less with respect to the total content of the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1) and the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3):

[0059]

[0060] [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15.

[0061]

[0062] [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent.

[0063]

[0064] [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

[0065] A fourteenth aspect of the present invention is a nonlinear optical element comprising a film formed from the composition of any one of the first to thirteenth aspects.

[0066] A fifteenth aspect of the present invention relates to the nonlinear optical element of the fourteenth aspect, which operates based on the electro-optic effect.

[0067] A sixteenth aspect of the present invention relates to an optical modulator comprising the nonlinear optical element according to the fourteenth or fifteenth aspect.

[0068] A seventeenth aspect of the present invention relates to a polymer compound comprising, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1) and a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3), wherein the content of the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3) is 0.0001 mol % or more and 25 mol % or less of the total content of the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1) and the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3):

[0069]

[0070] [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15.

[0071]

[0072] [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent.

[0073]

[0074] [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

[0075] Aspect 18 of the present invention relates to the polymer compound of aspect 17, wherein the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is at least R １４ and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) is at least R ３４ The present invention relates to a polymeric compound in which a hydrogen atom has been removed from the

[0076] Aspect 19 of the present invention is the polymer compound of aspect 17 or 18, wherein in the formula (3), Z ３１is a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a cyano group, an aldehyde group, or a carboxy group.

[0077] Aspect 20 of the present invention is a polymer compound according to any one of aspects 17 to 19, wherein Y in formula (1) １１ are each independently represented by the following formula (4), and Y in the formula (3) ３１ are each independently represented by the following formula (5), provided that n １１ When R is 2 or more, R in the following formula (4) ４１ and R ４２ is another Y １１ R included in ４１ or R ４２ may be linked to form a ring, and n in the formula (3) ３１ When R is 2 or more, R in the following formula (5) ５１ and R ５２ is another Y ３１ R included in ５１ or R ５２ and optionally linking to form a ring.

[0078]

[0079] [In formula (4), R ４１ and R ４２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ４１ and R４２ may be bonded to form a ring.

[0080]

[0081] [In formula (5), R ５１ and R ５２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ５１ and R ５２ may be bonded to form a ring.

[0082] Aspect 21 of the present invention is a polymer compound according to any one of aspects 17 to 20, wherein Y in formula (1) １１ and Y in the formula (3) ３１ are each independently represented by the following formula (6), the following formula (7), or the following formula (8), provided that n １１ When R is 2 or more, R in the following formula (6), the following formula (7), or the following formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y １１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７may be linked to form a ring, and n in the formula (3) ３１ When R is 2 or more, R in the following formula (6), the following formula (7), or the following formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y ３１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ and optionally linking to form a ring.

[0083]

[0084] [In formula (6), R ６１ and R ６２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ６１ and R ６２ may be bonded to form a ring.

[0085]

[0086] [In formula (7), R ７１ and R ７２are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ７１ and R ７２ may be bonded to form a ring, ７１ is O, S or N-Q ７１ and Q ７１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent.

[0087]

[0088] [In formula (8), R ８１ ~R ８７ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ８１ ~R ８７ At least two of these may be bonded to form a ring.

[0089] Aspect 22 of the present invention relates to the polymer compound of any one of aspects 17 to 21, wherein n in formula (1) １１ is n in the formula (3).３１ The polymer compound has a molecular weight of at least 1.

[0090] A twenty-third aspect of the present invention relates to a nonlinear optical element comprising a film formed from the polymer compound according to any one of aspects seventeen to twenty-second.

[0091] A twenty-fourth aspect of the present invention relates to the nonlinear optical element of the twenty-third aspect, which operates based on the electro-optic effect.

[0092] A twenty-fifth aspect of the present invention relates to an optical modulator comprising the nonlinear optical element according to the twenty-third or twenty-fourth aspect.

[0093] According to the present invention, it is possible to provide a composition and a polymer compound which can suppress the aggregation of dyes having a nonlinear optical effect in a nonlinear optical material and which exhibit a higher electro-optic effect relative to absorbance after poling. Furthermore, according to the present invention, it is possible to provide a nonlinear optical element using the composition, and an optical modulator which includes the nonlinear optical element and operates based on the electro-optic effect.

[0094] Explanation of Terms The terms used in this specification will be explained below.

[0095] <Polymer Compound> In this specification, a polymer compound refers to a compound having a molecular weight of 2000 or more and containing four or more identical repeating units in the molecule. The polymer compound is not particularly limited, but is preferably a polymer, and may be any of a homopolymer, a block copolymer, a random copolymer, an alternating copolymer, or a graft copolymer, or may be in other forms. The polymer compound according to an embodiment of the present invention can be used as a polymer compound having nonlinear optical activity. In this specification, the polymer compound according to an embodiment of the present invention may be referred to as a nonlinear optically active polymer compound.

[0096] <Copolymer> A copolymer refers to a polymer compound having two or more types of structural units in the molecule.

[0097] <Substituents> Unless otherwise specified, the substituents are any groups, but are preferably those selected from the following substituent group W １The substituents that may be present are selected from the group W １ The substituents selected from or optionally having are those in the substituent group W １ In the case where it is stated that the substituent is preferably selected from the following substituent group W １ As stated in the

[0098] <Substituent group W １ > Substituent group W １ is a group consisting of a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aromatic oxy group, an aralkyloxy group, an alkylthio group, an aromatic thio group, an aralkylthio group, an alkyloxycarbonyl group, a dialkylamino group, a diarylamino group, an arylalkylamino group, an acyl group, a halogen atom, a haloalkyl group, an alkylthio group, an arylthio group, a silyl group, a siloxy group, a cyano group, an aralkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. These substituents may have any of a linear, branched, and cyclic structure.

[0099] Substituent group W １More specifically, the following structures can be mentioned: A linear, branched, or cyclic alkyl group having 1 or more carbon atoms, preferably 4 or more, and usually 24 or less, preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, a dodecyl group, an adamantyl group, and the like. A linear, branched, or cyclic alkenyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a vinyl group, and the like. A linear or branched alkynyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include an ethynyl group, and the like. A linear, branched, or cyclic alkoxy group having 1 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, a dodecyloxy group, and an adamantyloxy group.

[0100] An aromatic oxy group having 4 or more carbon atoms, preferably 5 or more, and usually 36 or less, preferably 24 or less. Specific examples include a phenoxy group, a naphthoxy group, and a pyridyloxy group. An aralkyloxy group having 4 or more carbon atoms, preferably 5 or more, and usually 50 or less, preferably 30 or less. Specific examples include a benzyloxy group, a tolylmethoxy group, a thiophenylmethoxy group, a 2-phenylethyloxy group, a 2-phenylpropyl-2-yloxy group, a 2-phenylbutyl-2-yloxy group, a 3-phenylpentyl-3-yloxy group, a 3-phenyl-1-propyloxy group, a 4-phenyl-1-butyloxy group, a 5-phenyl-1-pentyoxyl group, a 6-phenyl-1-hexyloxy group, a 7-phenyl-1-heptyloxy group, and an 8-phenyl-1-octyloxy group.

[0101] An alkylthio group having 1 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, an n-butylthio group, an iso-butylthio group, a sec-butylthio group, a tert-butylthio group, an n-hexylthio group, a cyclohexylthio group, a dodecylthio group, and an adamantylthio group. An aromatic thio group having 3 or more carbon atoms, preferably 4 or more, and usually 50 or less, preferably 30 or less. Specific examples include a benzylthio group, a tolylthio group, and a thiophenylthio group. An aralkylthio group having 4 or more carbon atoms and usually 50 or less, preferably 30 or less. Specific examples include a benzylthio group, a tolylmethylthio group, a 2-phenylethylthio group, a 2-phenylpropyl-2-ylthio group, a 2-phenylbutyl-2-ylthio group, a 3-phenylpentyl-3-ylthio group, a 3-phenyl-1-propylthio group, a 4-phenyl-1-butylthio group, a 5-phenyl-1-pentylthio group, a 6-phenyl-1-hexylthio group, a 7-phenyl-1-heptylthio group, and an 8-phenyl-1-octylthio group.

[0102] An alkyloxycarbonyl group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a methoxycarbonyl group and an ethoxycarbonyl group. A dialkylamino group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a dimethylamino group and a diethylamino group. A diarylamino group having 10 or more carbon atoms, preferably 12 or more, and usually 36 or less, preferably 24 or less. Specific examples include a diphenylamino group, a ditolylamino group, an N-carbazolyl group, etc. An arylalkylamino group having 7 or more carbon atoms and usually 36 or less, preferably 24 or less. A specific example includes a phenylmethylamino group. An acyl group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include an acetyl group and a benzoyl group.

[0103] Halogen atoms such as fluorine, chlorine, bromine, and iodine atoms. Fluorine atoms are preferred. Haloalkyl groups having 1 or more carbon atoms and usually 12 or less, preferably 6 or less. Specific examples include a trifluoromethyl group. Alkylthio groups having 1 or more carbon atoms and usually 24 or less, preferably 12 or less. Specific examples include a methylthio group and an ethylthio group. Arylthio groups having 4 or more carbon atoms, preferably 5 or more, and usually 36 or less, preferably 24 or less. Specific examples include a phenylthio group, a naphthylthio group, and a pyridylthio group. Silyl groups having 2 or more carbon atoms, preferably 3 or more, and usually 36 or less, preferably 24 or less. Specific examples include a trimethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, and a triphenylsilyl group. Siloxy groups having 2 or more carbon atoms, preferably 3 or more, and usually 36 or less, preferably 24 or less, more preferably 18 or less. Specific examples include a trimethylsiloxy group, a tert-butyldimethylsiloxy group, a tert-butyldiphenylsiloxy group, and a triphenylsiloxy group.

[0104] An aralkyl group having usually 7 or more, preferably 9 or more, and usually 30 or less, preferably 18 or less, and more preferably 10 or less, carbon atoms. Specific examples include a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl-2-yl group, a 2-phenylbutyl-2-yl group, a 3-phenylpentyl-3-yl group, a 3-phenyl-1-propyl group, a 4-phenyl-1-butyl group, a 5-phenyl-1-pentyl group, a 6-phenyl-1-hexyl group, a 7-phenyl-1-heptyl group, and an 8-phenyl-1-octyl group. An aromatic hydrocarbon group having 6 or more, usually 36 or less, preferably 24 or less, carbon atoms. Specific examples include a phenyl group, a naphthyl group, and a group in which multiple phenyl groups are linked. An aromatic heterocyclic group having 3 or more, preferably 4 or more, carbon atoms and usually 36 or less, preferably 24 or less, carbon atoms. Specific examples include a thienyl group, a pyridyl group, and the like.

[0105] The substituents may have any of a linear, branched, or cyclic structure. When the substituents are adjacent to each other, the adjacent substituents may be bonded to each other to form a ring. The preferred ring size is a 4-membered ring, a 5-membered ring, or a 6-membered ring, and specific examples include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0106] <Alkyl Group> The alkyl group may have a substituent, and may be linear, branched, or cyclic. The number of carbon atoms is not usually limited, but preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 30 or less, and even more preferably 10 or less. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, a dodecyl group, an adamantyl group, and the like. The substituents that these groups may have are included in the substituent group W. １ is selected from.

[0107] <Aromatic Group> The aromatic group may have a substituent and represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and refers to a monovalent, divalent, or trivalent or higher valent structure depending on the bonding state in the structure of the compound to be described later. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0108] <Aromatic Hydrocarbon Group> The aromatic hydrocarbon group refers to a monovalent, divalent, or trivalent or higher aromatic hydrocarbon ring structure, depending on the bonding state in the structure of the compound to be described later. In the aromatic hydrocarbon ring structure, the number of carbon atoms is not usually limited, but is preferably 6 to 60 carbon atoms, with the upper limit of the carbon number being more preferably 48 or less carbon atoms, and even more preferably 30 or less carbon atoms. Specific examples include 6-membered monocyclic rings or fused ring groups containing 2 to 5 rings, such as benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings, or structures in which a plurality of groups selected from these are linked together. When a plurality of aromatic hydrocarbon rings are linked together, typically a structure in which 2 to 10 rings are linked together can be mentioned, with a structure in which 2 to 5 rings are linked together being preferred. When a plurality of aromatic hydrocarbon rings are linked, the linked rings may have the same structure or different structures.

[0109] <Aromatic heterocyclic group> The aromatic heterocyclic group refers to a monovalent, divalent, or trivalent or higher aromatic heterocyclic structure depending on the bonding state in the structure of the compound to be described later. In the heteroaromatic ring structure, the number of carbon atoms is not usually limited, but is preferably 3 to 50, and the upper limit of the carbon number is more preferably 45 or less, and even more preferably 30 or less. Specific examples thereof include a 5- or 6-membered single ring or a fused ring group containing 2 to 4 rings, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, or a quinazolinone ring, or a group in which a plurality of these rings are linked together. When a plurality of heteroaromatic rings are linked, the heteroaromatic rings may have the same structure or different structures. When a plurality of heteroaromatic rings are linked, typically, a structure in which 2 to 10 heteroaromatic rings are linked is mentioned, and a structure in which 2 to 5 heteroaromatic rings are linked is preferred.

[0110] <Amino Group> The amino group may have a substituent, and is preferably a secondary amino group, and more preferably a tertiary amino group. The substituent on the amino group is preferably an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and these groups may have a substituent. Furthermore, when the amino group has a plurality of substituents, these may be the same or different, and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. Specific examples include a dimethylamino group, a diethylamino group, an ethylmethylamino group, an n-propylmethylamino group, a di-isopropylamino group, a di-n-butylamino group, a di-n-hexylamino group, a di-n-butylamino group, a methylphenylamino group, an ethylphenylamino group, a butylphenylamino group, a hexylphenylamino group, a diphenylamino group, a 2,6-dimethylphenylphenylamino group, and a 2,4,6,trimethylphenylphenylamino group. The substituents that these groups may have are included in the substituent group W. １ is selected from.

[0111] <Halogen Atom> Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0112] <Alkyloxycarbonyl Group> The alkyloxycarbonyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an iso-propoxycarbonyl group, an n-butoxycarbonyl group, an iso-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, and a dodecyloxycarbonyl group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0113] <Alkylsulfonyl Group> The alkylsulfonyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an iso-propylsulfonyl group, an n-butylsulfonyl group, an iso-butylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, an n-hexylsulfonyl group, a cyclohexylsulfonyl group, and a dodecylsulfonyl group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0114] <Aralkyl Group> The aralkyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl-2-yl group, a 2-phenylbutyl-2-yl group, a 3-phenylpentyl-3-yl group, a 3-phenyl-1-propyl group, a 4-phenyl-1-butyl group, a 5-phenyl-1-pentyl group, a 6-phenyl-1-hexyl group, a 7-phenyl-1-heptyl group, and an 8-phenyl-1-octyl group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0115] <Boryl group> The boryl group may have a substituent, and is preferably a secondary boryl group, more preferably a tertiary boryl group. The substituent that the boryl group has is preferably a hydroxy group, an alkyloxycarbonyl group, an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and these groups may have a substituent. Furthermore, when the boryl group has a plurality of substituents, they may be the same or different, and may be bonded to each other to form a ring together with the boron atom to which each is bonded. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0116] <Acyl group> The acyl group may have a substituent, and the number of carbon atoms is not usually limited, but preferably has 2 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 24 or less, and even more preferably 12 or less. Specific examples include a benzoyl group and an acetyl group. The substituents that these groups may have are included in the substituent group W. １ is selected from.

[0117] <Alkoxy Group> The alkoxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, and a dodecyloxy group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0118] <Aromatic Oxy Group> The aromatic oxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. Specific examples include a naphthoxy group and a thiophenyloxy group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0119] <Aralkyloxy Group> The aralkyloxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 4 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzyloxy group, a tolylmethoxy group, a thiophenylmethoxy group, a 2-phenylethyloxy group, a 2-phenylpropyl-2-yloxy group, a 2-phenylbutyl-2-yloxy group, a 3-phenylpentyl-3-yloxy group, a 3-phenyl-1-propyloxy group, a 4-phenyl-1-butyloxy group, a 5-phenyl-1-pentyoxyl group, a 6-phenyl-1-hexyloxy group, a 7-phenyl-1-heptyloxy group, and an 8-phenyl-1-octyloxy group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0120] <Alkylthio Group> The alkylthio group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 1 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, an n-hexylthio group, a cyclohexylthio group, and a dodecylthio group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0121] <Aromatic Thio Group> The aromatic thio group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzylthio group, a tolylthio group, and a thiophenylthio group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0122] <Aralkylthio Group> The aralkyloxy group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 4 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 30 or less, and even more preferably 20 or less. Specific examples include a benzylthio group, a tolylmethylthio group, a 2-phenylethylthio group, a 2-phenylpropyl-2-ylthio group, a 2-phenylbutyl-2-ylthio group, a 3-phenylpentyl-3-ylthio group, a 3-phenyl-1-propylthio group, a 4-phenyl-1-butylthio group, a 5-phenyl-1-pentylthio group, a 6-phenyl-1-hexylthio group, a 7-phenyl-1-heptylthio group, and an 8-phenyl-1-octylthio group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0123] <Silyl Group> The silyl group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a trimethylsilyl group, a triethylsilyl group, a propyldimethylsilyl group, a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl group. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0124] <Hydrocarbon Ring Group> The hydrocarbon ring group is a cyclic hydrocarbon group which may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, with the upper limit of the carbon number being more preferably 20 or less, and even more preferably 10 or less. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a group in which a plurality of these groups are linked together.

[0125] <Branched, linear or cyclic saturated or unsaturated hydrocarbon chain, some of whose carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms> The branched, linear or cyclic saturated or unsaturated hydrocarbon chain, some of whose carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, refers to a carbon chain consisting of a branched, linear or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 15 carbon atoms, in which some of the carbon chain may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms. Specific examples include the following groups.

[0126] Specific examples of unsubstituted groups include hydrocarbon chains of 1 to 15 carbon atoms, more specifically methyl groups, ethyl groups, 1-butyl groups, tert-butyl groups, cyclopentyl groups, 4-ethyl-1-cyclohexyl groups, 2-penten-1-yl groups, 1-octyl groups, 1-decyl groups, etc., with methyl groups, ethyl groups, and 1-butyl groups being preferred. Specific examples of groups substituted with oxygen atoms include 2-ethoxyethyl groups, 2-(2-ethoxyethoxy)ethyl groups, 2-hydroxyethyl groups, and tetrahydropyranyloxypropyl groups, with 2-ethoxyethyl groups and 2-hydroxyethyl groups being preferred, and 2-hydroxyethyl groups being particularly preferred. Specific examples of groups substituted with sulfur atoms include 2-ethylthioethyl groups, tetrahydrothienyl groups, and 2-(2-ethylthioethylthio)ethyl groups. Specific examples of groups substituted with silicon atoms include trimethylsilyl groups and tert-butyldimethylsilyl groups. These may also be substituted with oxygen atoms or silicon atoms at the same time, and specific examples thereof include a 2-(trimethylsilyloxy)ethyl group, a 2-(tert-butyldimethylsilyloxy)ethyl group, a 4-(tert-butyldimethylsilyloxy)butyl group, a 2-(tert-butyldiphenylsilyloxy)ethyl group, and a 2-(tert-butyldimethylsilyloxy)hexyl group, and preferably a 2-(tert-butyldimethylsilyloxy)ethyl group and a 4-(tert-butyldimethylsilyloxy)butyl group. The substituents that these groups may have are those in the substituent group W １is selected from.

[0127] <Heterocyclic Group> The heterocyclic group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 3 to 50 carbon atoms, and the upper limit of the number of carbon atoms is more preferably 20 or less, and even more preferably 10 or less. Specific examples include a thiane group, a 1,4-dithiane group, a tetrahydrofuran group, a tetrahydropyran group, a pyran group, a 1,4-dioxane group, or a group in which a plurality of these groups are linked together. The substituents that these groups may have are included in the substituent group W １ is selected from.

[0128] <π-conjugated linking group> The π-conjugated linking group is a divalent group in the structure of a compound to be described later, which is composed of alternately connected single bonds and multiple bonds and has delocalized electrons (π electrons). The π-conjugated linking group may have a substituent, and although the number of carbon atoms is not usually limited, it preferably has 2 to 50 carbon atoms, and the upper limit of the carbon number is more preferably 30 or less, and even more preferably 20 or less. In addition, the substituents of multiple π-conjugated groups may be bonded to form a cyclic structure. Specific examples include vinylene, thiophene, furan, pyrrole, etc. The substituents that these groups may have are represented by the substituent group W. １ is selected from.

[0129] <Blocked Isocyanate Group> A blocked isocyanate group is an isocyanate group protected with a blocking agent. It remains stable under normal conditions, and heat treatment dissociates the blocking agent, regenerating the isocyanate group. The group selected as the blocking agent is not particularly limited, but may have from 1 to 50 carbon atoms, with the upper limit of the carbon number being preferably 30 or less, and even more preferably 20 or less. Furthermore, the substituents of multiple π-conjugated groups may be bonded to form a cyclic structure. Specific examples include a methylethyloxime group, a 3,5-dimethylpyrazolyl group, and an ε-caprolactam group. A dimethylpyrazole group is preferred. The heat treatment temperature required for dissociation of the blocking agent is not particularly limited, as it varies depending on the catalyst and reaction conditions, but is generally 20°C to 250°C. The lower limit is preferably 40°C or higher, more preferably 60°C or higher, and most preferably 100°C or higher, while the upper limit is preferably 250°C or lower, more preferably 200°C or lower.

[0130] <Nonlinear Optical Material> The nonlinear optical material in this embodiment is made of a nonlinear optically active compound, a nonlinear optically active polymer compound, or both.

[0131] <Nonlinear Optically Active Compound> The nonlinear optically active compound in this embodiment is a compound represented by formula (1) (also referred to as a dye) or formula (3) (also referred to as a secondary dye).

[0132] <Nonlinear Optically Active Polymer Compound> The nonlinear optically active polymer compound in this embodiment is formed by bonding a group in which at least one hydrogen atom has been removed from a compound represented by formula (1) and / or a group in which at least one hydrogen atom has been removed from a compound represented by formula (3) to a repeating unit in the polymer compound.

[0133] The polymer compound is not particularly limited, but specific examples include poly(meth)acrylic acid esters (e.g., polymethyl methacrylate (PMMA), polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), polycarbonylaminoethyl methacrylate, etc.), polyamide, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, polycarbonate, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyester, polyolefin, polyphenylene sulfide, aromatic polyamine, polyamine, polyurea, silicone-based resin, epoxy-based resin, polyvinyl chloride, fluoropolymer, and copolymers thereof. (Meth)acrylic refers to at least one selected from acrylic and methacrylic. The same applies to (meth)acrylates and the like.

[0134] In particular, from the viewpoint of general excellence as an optical material, at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, and copolymers thereof is more preferred, and from the viewpoint of compound stability, polystyrene, polymethacrylic acid esters, and maleimide-styrene copolymers are most preferred. Preferred examples of polymethacrylic acid esters include polyadamantyl methacrylate (polyAdMA), polyalkyloxycarbonylaminoethyl methacrylate, polymethyl methacrylate (PMMA), and poly(cyclic or linear) alkyl methacrylates.

[0135] <Explanation of Bond Form> The bond form between the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and / or the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) and the polymer compound is not particularly limited, and is, for example, bonded via a (thio)urethane bond, a (thio)urea bond, a (thio)amide bond, a carbon-carbon bond, a (thio)ester bond, a (thio)ether bond, etc. (Thio)urethane means at least one selected from urethane and thiourethane, and the same applies to (thio)urea, (thio)ester, (thio)ether, and (thio)amide. In particular, from the viewpoint of compound stability, a urethane bond, a carbon-carbon bond, an ester bond, or an ether bond is preferred, and an ester bond or an ether bond is most preferred.

[0136] The group obtained by removing at least one hydrogen atom from the compound represented by formula (1) or formula (3) is -W ５１ -X ５１ The -W may be contained in the polymer compound as at least one selected from a substituent and a main chain via a linking group represented by -. ５１ -X ５１ - If present, W ５１ or X ５１ Either one of the above bonds to the element from which the hydrogen atom in formula (1) or formula (3) has been removed.

[0137] (W ５１ ) W ５１ represents a single bond, a carbonyl group, a thionyl group, a phenyl group, or a triazole group.

[0138] (X ５１ ) X ５１ represents a single bond, an oxygen atom, a sulfur atom, a phenyl group, or an —NH— group.

[0139] (Example Structure) -W ５１ -X ５１ Examples of the structure represented by - include, but are not limited to, structures represented by formulae (W-X)-1 to (W-X)-12. * in formulae (W-X)-1 to (W-X)-12 indicates a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) or formula (3), and indicates the bonding position with the repeating structure of the polymer compound.

[0140]

[0141] The number of bonds to the polymer compound per group derived from the compound represented by formula (1) and / or formula (3) is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1. That is, in one embodiment, the nonlinear optically active polymer compound can be obtained by bonding to the polymer compound a group obtained by removing preferably 1 to 3, more preferably 1 to 2 hydrogen atoms from the compound represented by formula (1) and / or formula (3). The site having the removed hydrogen atom in the group derived from the compound represented by formula (1) and / or formula (3) is not particularly limited as long as it is a substituent having a hydrogen atom, but can be any of R in formula (1). １１ , R １２ , R １３ , R １４ , and / or Y １１ and / or R in formula (3) ３１ , R ３２ , R ３３ , R ３４ , and / or Y ３１ is preferably a hydrogen atom possessed by R in formula (1). １１ , R １２ , R １３ , or R １４ and / or R in formula (3) ３１ , R ３２ , R ３３ , or R ３４ It is more preferable that R in formula (1) is a hydrogen atom. １４ and / or R in formula (3) ３４ It is most preferable that the hydrogen atom is a hydrogen atom possessed by

[0142] <Crosslinking Group> The polymer compound according to this embodiment may have a crosslinking group. By having a crosslinking group, crosslinking can be performed after poling treatment, thereby improving the durability of the compound. Examples of the crosslinking group include a vinyl group, an acryloyl group, a methacryloyl group, an allyl group, a thiol group, a polyamine, a polyol, an isocyanate group, a cyanoacryloyl group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group, an α-methylcinnamylidene group, an α-methylcinnamylidene acetyl group, an α,γ-dimethylcinnamylidene group, an α,γ-dimethylcinnamylidene acetyl group, an α-phenylcinnamylidene group, an α-phenylcinnamylidene acetyl group, an α-phenoxycinnamylidene group, an α-phenoxycinnamylidene acetyl group, an α-cyanocinnamylidene group, an α-cyanocinnamylidene acetyl group, a chalcone residue, an oxetane group, an epoxy group, an isocoumarin residue, a 2,5-dimethoxystilbene residue, a thymine residue, a stilpyridinium residue, a maleimide residue, an α-phenylmaleimide residue, an anthracene residue, a 2-pyridinyl group ... Examples of the alkyl group include a methyl group, a vinyl ether group, a trifluorovinyl ether group, a benzocyclobutene group, a 1-phenyloxybenzocyclobutene group, and derivatives thereof. Preferred examples include an acryloyl group, a methacryloyl group, a thiol group, an isocyanate group, a blocked isocyanate group, a cinnamoyl group, a cinnamylidene group, an α-cyanocinnamylidene group, an anthracene residue, a maleimide residue, a benzocyclobutene group, and a 1-phenyloxybenzocyclobutene group. More preferred examples include an acryloyl group, a thiol group, an isocyanate group, a blocked isocyanate group, an anthracene residue, a maleimide residue, a benzocyclobutene group, and a 1-phenyloxybenzocyclobutene group. Particularly preferred examples include an acryloyl group, an isocyanate group, a blocked isocyanate group, an anthracene residue, a maleimide residue, and a 1-phenyloxybenzocyclobutene group.

[0143] The polymer compound according to this embodiment may have a repeating unit containing a crosslinking group. By having a repeating unit containing a crosslinking group, crosslinking can be performed after poling treatment, improving the durability of the compound. Examples of the crosslinking group include the crosslinking groups described above, and preferred crosslinking groups are also as described above.

[0144] <Examples of repeating units containing a crosslinking group> Preferred specific examples of repeating units (CL) containing a crosslinking group are shown below, but the present invention is not limited thereto.

[0145]

[0146] The content of the group derived from the nonlinear optically active compound in the nonlinear optically active polymeric compound can be expressed as the ratio of the mass of the entire nonlinear optically active polymeric compound to the mass of the group derived from the compound represented by the nonlinear optically active compound, or can be expressed as the molar percentage of the compound derived from the nonlinear optical compound to the total of each repeating unit of the nonlinear optically active polymeric compound. When expressed as a mass ratio, there are no particular restrictions on the content of the group derived from the nonlinear optical compound in the nonlinear optically active polymeric compound, but from the viewpoint of the balance between the electro-optical effect and solubility, when the mass of the entire nonlinear optically active polymeric compound is taken as 100, the lower limit of the mass of the group derived from the nonlinear optical compound is preferably 1 or more, more preferably 10 or more, and even more preferably 20 or more, and the upper limit is preferably 80 or less, more preferably 60 or less, and even more preferably 50 or less.

[0147] When the content of the group derived from the nonlinear optically active compound in the nonlinear optically active polymer compound is expressed as a molar percentage, there are no particular limitations, but from the viewpoint of the balance between the electro-optical effect and solubility, the molar percentage of the group derived from the nonlinear optical compound relative to the total of all repeating units of the nonlinear optically active polymer compound is preferably 0.1 mol% or more as a lower limit, more preferably 1 mol% or more, and even more preferably 2 mol% or more as an upper limit, preferably 60 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less.

[0148] The content of the group derived from the nonlinear optically active compound in the nonlinear optically active polymer compound is １ It is calculated by H-NMR, absorbance measurement, gel permeation chromatography (GPC) or the like, but preferably, １ H-NMR, absorbance measurement, most preferably １ The content of the compound derived from formula (3) relative to the compound derived from formula (1) can be calculated in the same manner.

[0149] １ A specific method for calculating the content of groups derived from a nonlinear optically active compound in a nonlinear optically active polymeric compound by H-NMR is to use a spectral integral value derived from specific hydrogen atoms in the nonlinear optically active compound as a reference and calculate the ratio of the spectral integral value derived from specific hydrogen atoms in the groups possessed by each repeating unit of the nonlinear optically active polymeric compound to calculate the molar ratio of the nonlinear optically active compound to each repeating unit of the nonlinear optically active polymeric compound. From this molar ratio, the apparent mass ratio can be calculated, and the content of groups derived from the nonlinear optically active compound in the nonlinear optically active polymeric compound can be calculated.

[0150] A specific method for calculating the content of groups derived from nonlinear optically active compounds in a nonlinear optically active polymer compound by absorbance measurement is to calculate the ratio of the maximum absorbance measured using a solution in which the nonlinear optically active compound is dissolved at a predetermined concentration to the concentration, and the value obtained by similarly measuring the absorbance of the nonlinear optically active polymer compound. The absorbance is measured using an ultraviolet-visible-near-infrared spectrophotometer. In addition, when multiple types of nonlinear optically active compounds are contained (for example, when a dye and a sub-dye are contained), the absorbance obtained by measuring the absorbance of a nonlinear optically active polymer compound (the content of which is known) containing each nonlinear optically active compound alone is weighted (X ｎ ) and the sum of the absorbance (normalized by the maximum absorbance, I ｎ ​The weighting is changed so that the residual sum of squares (RSS) over all measured wavelengths of the absorbance (normalized by the maximum absorbance, referred to as ActI) obtained by measuring the absorbance of a nonlinear optically active compound containing multiple types of nonlinear optically active compounds is minimized, and the content of each nonlinear optically active compound is calculated from the obtained weighting.

[0151]

[0152]

[0153] [In the above formula, λ represents the number of measurement wavelengths, and n represents the number of nonlinear optically active compound species contained.]

[0154] The content can be calculated by substituting Xn obtained from the above formula into the following formula: Content = [content of nonlinear optically active compound in nonlinear optically active polymer compound containing only the nonlinear optically active compound] × X ｎ

[0155] The weight-average molecular weight of the nonlinear optically active polymer compound is not particularly limited, but is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 30,000 or more in order to improve durability. In addition, in order to improve solubility, it is preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less. The weight-average molecular weight of the nonlinear optically active polymer compound is confirmed by measuring the weight-average molecular weight using polystyrene as a standard by GPC.

[0156] There are no particular restrictions on the molecular weight distribution of the nonlinear optically active polymer compound, but it is preferably 3 or less, more preferably 2.8 or less, and even more preferably 2.5 or less. From the viewpoint of improving performance, it is preferable that the molecular weight distribution of the nonlinear optically active polymer compound is 3 or less. The molecular weight distribution of the nonlinear optically active polymer compound is confirmed by measuring the ratio of the number average molecular weight to the weight average molecular weight using GPC when polystyrene is used as a standard.

[0157] The glass transition temperature (Tg) of the nonlinear optically active polymer compound is not particularly limited, but is generally 40°C to 300°C. To improve heat resistance, the Tg is preferably 45°C or higher, more preferably 50°C or higher, and even more preferably 80°C or higher. From the viewpoint of the poling process, the Tg is preferably 280°C or lower, more preferably 250°C or lower, and even more preferably 230°C or lower. The Tg of the nonlinear optically active polymer compound is confirmed by measuring the temperature corresponding to the intersection of the slope of the rising part of the endothermic process and the baseline of the baseline shift of the DSC curve accompanying the glass transition using a differential scanning calorimeter (DSC).

[0158] The decomposition temperature (Td) of the nonlinear optically active polymer compound is not particularly limited, but is preferably 0°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. It is also preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower. The Td of the nonlinear optically active polymer compound is confirmed by measuring the temperature at which the mass decreases by 5% using a thermogravimetric differential thermal analyzer (TG-DTA).

[0159] <Dye and Sub-Dye> In the examples described later, the dye represents a compound represented by formula (1), and the sub-dye represents a compound represented by formula (3).

[0160] <Explanation of Formula (1)>

[0161]

[0162] [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R１４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15.

[0163] (Ar １１ ) Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent.

[0164] Examples of the aromatic hydrocarbon group include rings having a carbon number of usually 6 or more and usually 60 or less, preferably 30 or less, more preferably 18 or less, and even more preferably 10 or less, such as a benzene ring, naphthalene ring, anthracene ring, tetraphenylene ring, phenanthrene ring, chrysene ring, pyrene ring, benzanthracene ring, or perylene ring. In order to fix the molecular structure by hydrogen bonding with the adjacent π-conjugated linking group, a benzene ring or naphthalene ring having an alkoxy group or aralkyloxy group is particularly preferred.

[0165] Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, or a quinazolinone ring, each of which typically has 3 or more carbon atoms and typically has 50 or less, preferably 45 or less, more preferably 30 or less, and even more preferably 12 or less. A thiophene ring is particularly preferred for shifting the absorption wavelength of the dye to a longer wavelength. In order to fix the molecular structure by hydrogen bonding with the adjacent π-conjugated linking group, a heterocycle having an alkoxy group or an aralkyloxy group is particularly preferred. １１ The substituents which may be contained in the group W １ It is preferably selected from:

[0166] (R １１ and R １３ ) R １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, some of whose carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have a substituent. １１ and R １３ The substituents which may be contained in the group W １ It is preferably selected from:

[0167] (R １２ and R １４ ) R １２ and R １４are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain of 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group of 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group of 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group, or a halogen atom. １２ and R １４ The substituents which may be contained in the group W １ It is preferably selected from:

[0168] (Y １１ ) Y １１ Each of Y is independently a divalent π-conjugated linking group which may have a substituent. １１ If there are multiple Y １１ may have the same structure or different structures. １１ The plurality of substituents of may form a bond to form a cyclic structure. Examples of the π-conjugated linking group include groups having carbon atoms of usually 2 or more and usually 50 or less, preferably 30 or less, and more preferably 20 or less, such as vinylene which may have a substituent, thiophene which may have a substituent, furan which may have a substituent, and pyrrole which may have a substituent. １１ The substituents which may be contained in the group W １ It is preferably selected from:

[0169] (Z １１ ) Z １１ is a group represented by formula (2) described below.

[0170] (m １１ ~m １３ , n １１ ) m １１ are each independently an integer of 0 to 5, and m １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, and n １１ is an integer from 1 to 15. １１is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably an integer of 0 to 2. １２ is preferably an integer of 1 to 4, more preferably an integer of 1 to 3. １３ is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably an integer of 0 to 2. From the viewpoint of improving the nonlinear optical properties of the dye, n １１ is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and from the viewpoint of reducing absorption loss, is preferably 14 or less, more preferably 13 or less, and even more preferably 10 or less.

[0171] (Exemplary Compounds) Examples of compounds represented by formula (1) include, but are not limited to, compounds represented by formulas (1)-1 to (1)-256. These compounds may further have a substituent.

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200] <Explanation of Formula (2)>

[0201]

[0202] [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent.

[0203] (*J ２１ ) *J ２１ Is Y １１ This is the bonding position with

[0204] (R ２１ and R ２２ ) R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are bonded. ２１ and R ２２ The substituent of R is preferably a fluorine atom, a chlorine atom, a bromine atom, or a cyano group. ２１ and R ２２ The substituents which may be contained in the group W １ It is preferably selected from:

[0205] (R ２３ and R ２４ ) R ２３ and R ２４ are each independently a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent. A cyano group is preferred. ２３ and R ２４ The substituents which may be contained in the group W １ It is preferably selected from:

[0206] (X ２１ ) X ２１ is O, S or N-Q ２１ Preferably O or NQ ２１ and more preferably O.

[0207] (Q ２１ ) Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent. ２１ The substituents which may be contained in the group W １ It is preferably selected from:

[0208] (Exemplary Structure) Examples of the structure represented by formula (2) include, but are not limited to, structures represented by formulas (2)-1 to (2)-35. These compounds may further have a substituent.

[0209]

[0210]

[0211] <Explanation of Formula (3)>

[0212]

[0213] [In formula (3), Ar ３１are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

[0214] (Ar ３１ ) Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent.

[0215] Examples of the aromatic hydrocarbon group include rings having a carbon number of usually 6 or more and usually 60 or less, preferably 30 or less, more preferably 18 or less, and even more preferably 10 or less, such as a benzene ring, naphthalene ring, anthracene ring, tetraphenylene ring, phenanthrene ring, chrysene ring, pyrene ring, benzanthracene ring, or perylene ring. In order to fix the molecular structure by hydrogen bonding with the adjacent π-conjugated linking group, a benzene ring or naphthalene ring having an alkoxy group or aralkyloxy group is particularly preferred.

[0216] Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, or a quinazolinone ring, each of which typically has 3 or more carbon atoms and typically has 50 or less, preferably 45 or less, more preferably 30 or less, and even more preferably 12 or less. A thiophene ring is particularly preferred for shifting the absorption wavelength of the dye to a longer wavelength. In order to fix the molecular structure by hydrogen bonding with the adjacent π-conjugated linking group, a heterocycle having an alkoxy group or an aralkyloxy group is particularly preferred. ３１ The substituents which may be contained in the group W １ It is preferably selected from:

[0217] (R ３１ and R ３３ ) R ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, some of whose carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms, which may have a substituent. ３１ and R ３３ The substituents which may be contained in the group W １ It is preferably selected from:

[0218] (R ３２ and R ３４ ) R ３２ and R ３４are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain of 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group of 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group of 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group, or a halogen atom. ３２ and R ３４ The substituents which may be contained in the group W １ It is preferably selected from:

[0219] (Y ３１ ) Y ３１ Each of Y is independently a divalent π-conjugated linking group which may have a substituent. ３１ If there are multiple Y ３１ may have the same structure or different structures. ３１ The plurality of substituents of may form a bond to form a cyclic structure. Examples of the π-conjugated linking group include groups having carbon atoms of usually 2 or more and usually 50 or less, preferably 30 or less, and more preferably 20 or less, such as vinylene which may have a substituent, thiophene which may have a substituent, furan which may have a substituent, and pyrrole which may have a substituent. ３１ The substituents which may be contained in the group W １ It is preferably selected from:

[0220] (Z ３１ ) Z ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. More preferred are a hydrogen atom, a branched, linear, or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, a halogen atom, a cyano group, an aldehyde group, or a carboxy group. Even more preferred are an aldehyde group, a cyano group, or a carboxy group. However, Z ３１ does not include the group represented by formula (2). ３１ The substituents which may be contained in the group W １ It is preferably selected from:

[0221] (R ３５ and R ３６ ) R ３５ and R ３６ R are each independently an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent. ３５ and R ３６ The substituents which may be contained in the group W １ It is preferably selected from:

[0222] (m ３１ ~m ３３ , n ３１ ) m ３１ are each independently an integer of 0 to 5, and m ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, and n ３１ is an integer from 0 to 15. ３１ If is 0, the aforementioned Z ３１ is not a hydrogen atom. ３１ is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably an integer of 0 to 2. ３２ is preferably an integer of 1 to 4, more preferably an integer of 1 to 3. ３３is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and even more preferably an integer of 0 to 2. From the viewpoint of the number of manufacturing steps, n ３１ is preferably an integer of 0 to 14, more preferably an integer of 0 to 13, and even more preferably an integer of 0 to 10.

[0223] (Exemplary Compounds) Examples of compounds represented by formula (3) include, but are not limited to, compounds represented by formulas (3)-1 to (3)-328. These compounds may further have a substituent.

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257] <Explanation of Formula (4)>

[0258]

[0259] [In formula (4), R ４１ and R ４２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ４１ and R ４２may be bonded to form a ring.

[0260] (R ４１ and R ４２ ) R ４１ and R ４２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ４１ and R ４２ may be bonded to form a ring. ４１ and R ４２ The substituents which may be contained in the group W １ It is preferably selected from:

[0261] <Explanation of Formula (5)>

[0262]

[0263] [In formula (5), R ５１ and R ５２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ５１ and R ５２ may be bonded to form a ring.

[0264] (R ５１ and R ５２ ) R ５１ and R ５２are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ５１ and R ５２ may be bonded to form a ring. ５１ and R ５２ The substituents which may be contained in the group W １ It is preferably selected from:

[0265] <Explanation of Formula (6)>

[0266]

[0267] [In formula (6), R ６１ and R ６２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ６１ and R ６２ may be bonded to form a ring.

[0268] (R ６１ and R ６２ ) R ６１ and R ６２are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ６１ and R ６２ may be bonded to form a ring. ６１ and R ６２ The substituents which may be contained in the group W １ It is preferably selected from:

[0269] <Explanation of Formula (7)>

[0270]

[0271] [In formula (7), R ７１ and R ７２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ７１ and R ７２ may be bonded to form a ring, ７１ is O, S or N-Q ７１ and Q ７１is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent.

[0272] (R ７１ and R ７２ ) R ７１ and R ７２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ７１ and R ７２ may be bonded to form a ring. ７１ and R ７２ The substituents which may be contained in the group W １ It is preferably selected from:

[0273] (X ７１ ) X ７１ is O, S or N-Q ７１ Preferably, it is O or S, and more preferably S.

[0274] (Q ７１ ) Q ７１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent. ７１The substituents which may be contained in the group W １ It is preferably selected from:

[0275] <Explanation of Formula (8)>

[0276]

[0277] [In formula (8), R ８１ ~R ８７ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ８１ ~R ８７ At least two of these may be bonded to form a ring.

[0278] (R ８１ ~R ８７ ) R ８１ ~R ８７ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ８１ ~R ８７ At least two of R may be bonded to form a ring. ８１ is an alkoxy group, and R ８２ ~R ８７R is a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, which may have a hydrogen atom or a substituent, and some of the carbon atoms may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms. ８１ ~R ８７ The substituents which may be contained in the group W １ It is preferably selected from:

[0279] <Composition> The composition of this embodiment contains the nonlinear optical material described above. The composition of this embodiment may further contain an organic solvent and / or a polymer material. In particular, when the nonlinear optical material contains the compounds represented by the above formula (1) and the above formula (3), it is preferable that the composition further contains a polymer material.

[0280] <Solid content> The solid content refers to the amount of components other than the organic solvent contained in the composition. Note that even if a component other than the organic solvent is liquid at room temperature, that component is not included in the organic solvent but is included in the solid content.

[0281] <Composition Comprising a Compound Represented by Formula (1) and a Compound Represented by Formula (3), Which Are Nonlinear Optically Active Compounds> A composition according to an embodiment of the present invention comprises a compound represented by the above formula (1) and a compound represented by the above formula (3). The composition may further comprise an organic solvent. Preferred aspects of the composition are described in detail below. In addition, in the composition according to an embodiment of the present invention, the definitions and preferred ranges of each group contained in formulas (1) and (3), as well as formulas (2) and (4) to (8) described below, are as described for formulas (1) to (8) above.

[0282] From the viewpoint of optimizing the dipole moment of the compound, the composition according to the embodiment of the present invention is １１ are each independently represented by the above formula (4), and Y in the above formula (3) ３１ are each independently represented by the above formula (5), provided that n １１ When R is 2 or more, ４１ and R ４２ is another Y １１ R included in４１ or R ４２ may be linked to form a ring, and n in the above formula (3) ３１ When R is 2 or more, ５１ and R ５２ is another Y ３１ R included in ５１ or R ５２ and may be linked to form a ring.

[0283] From the viewpoint of optimizing the dipole moment of the compound, the composition according to the embodiment of the present invention is １１ and Y in the above formula (3) ３１ are each independently represented by the above formula (6), the above formula (7), or the above formula (8), provided that n １１ When R is 2 or more, R in the above formula (6), the above formula (7), or the above formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y １１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ may be linked to form a ring, and n in the above formula (3) ３１ When R is 2 or more, R in the above formula (6), the above formula (7), or the above formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７is another Y ３１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ and may be linked to form a ring.

[0284] In order to optimize the mass ratio of the dye to the auxiliary dye, n １１ is n in the above formula (3) ３１ It is preferably 1 or more larger than 1, more preferably 1 to 5 larger, and even more preferably 1 to 3 larger.

[0285] From the viewpoint of improving the compatibility between the dye and the auxiliary dye, Z １１ and Z in the above formula (3) ３１ , R in the above formula (1) １４ and R in the above formula (3) ３４ , and Y in formula (1) １１ and Y in the above formula (3) ３１ The structure of the compound represented by the formula (1) is the same as the structure of the compound represented by the formula (3), or １１ and Y in the above formula (3) ３１ are preferably the same, and Z １１ and Z in the above formula (3) ３１ , and R in the above formula (1) １４ and R in the above formula (3) ３４ It is more preferable that the structure of the compound represented by the above formula (1) and the structure of the compound represented by the above formula (3) are identical, except for the following:

[0286] In order to optimize the dipole moment of the compound, Z ３１ is a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５, -C(O)N(R ３５ ) (R ３６ ), a cyano group, an aldehyde group, or a carboxy group, and particularly preferably an aldehyde group or a cyano group.

[0287] (Polymer Material) From the viewpoint of improving the heat resistance of the composition, the composition according to the embodiment of the present invention preferably contains a polymer material. There are no particular limitations on the polymer material as long as it can disperse the nonlinear optically active compound, but a transparent polymer that does not scatter light is preferred for use as an optical material, and examples thereof include (meth)acrylate polymers (e.g., polymethyl methacrylate (PMMA)), polyamide, polyimide, polycarbonate, polydicyclopentanyl methacrylate (poly DCPMA), and polyadamantyl methacrylate (poly Examples of the polymer include poly(DCPMA-co-MMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), etc.), cycloolefin polymers, cycloolefin copolymers, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyester, polyolefin, polyphenylene sulfide, polyurea, silicone resins, epoxy resins, polyvinyl chloride, fluororesins, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, norbornene-maleimide copolymers, polynorbornene, and copolymers thereof. Among these, from the viewpoint of molecular orientation, at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, and copolymers thereof is preferred. The poly(meth)acrylic acid ester is preferably polymethyl(meth)acrylate.The organic polymers may be used singly or in combination of two or more.

[0288] [Organic Solvent] From the viewpoint of improving the processability of the composition, it is preferable that the composition according to the embodiment of the present invention contains an organic solvent. The organic solvent that can be used in the composition is not particularly limited as long as it can dissolve the compound represented by the above formula (1) and the compound represented by the above formula (3). For example, aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and styrene; aliphatic hydrocarbons such as n-hexane and n-heptane; halogenated hydrocarbons such as chlorobenzene, orthodichlorobenzene, chloroform, dichloromethane, dibromomethane, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxybenzotrifluoride, and 3-methoxybenzotrifluoride; ketones such as acetone, ethyl methyl ketone, isopropyl methyl ketone, isobutyl methyl ketone, butyl methyl ketone, diacetone alcohol, diethyl ketone, cyclopentanone, and cyclohexanone; ethyl acetate, propyl acetate, phenyl acetate, 2-methoxyethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethyl lactate, γ-butyl acetate, methyl ketone ... Esters such as chloractone, ethyl benzoate, methyl benzoate, benzoyl benzoate, 2-ethylhexyl benzoate, and ethyl 4-methylbenzoate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; alcohols such as methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, 2-methylbutanol, 2-methyl-2-butanol, cyclohexanol, 2-methylpentanol, octanol, 2-ethylhexanol, benzyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; glycols such as ethylene glycol, propylene glycol, hexylene glycol, trimethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol;Examples of suitable organic solvents include ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide, and anisole. These organic solvents may be used alone or in combination of two or more.

[0289] Of the above organic solvents, from the viewpoint of coatability, chlorobenzene, orthodichlorobenzene, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxybenzotrifluoride, 3-methoxybenzotrifluoride, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are more preferable, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are even more preferable, and cyclopentanone, cyclohexanone, toluene, anisole, and dibromomethane are particularly preferable.

[0290] (Other Components) The composition according to the embodiment of the present invention may contain other components in addition to those described above. The components that the composition may further contain are not particularly limited as long as they do not impair the purpose of using the composition, but as long as they do not impair the effects of the present invention, they may contain, as necessary, antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesion aids such as silane coupling agents, crosslinkers for polymer matrices, compatibilizers, curing agents, pigments, storage stabilizers, antifoaming agents, etc.

[0291] (Content) There are no particular limitations on the content of each component in the composition according to the embodiment of the present invention.

[0292] Although there are no particular restrictions on the content of the nonlinear optically active compound in the composition, the content of the component exhibiting nonlinear optical activity is preferably 1 to 100 mass %, more preferably 5 to 100 mass %, and even more preferably 10 to 100 mass %, relative to 100% of the solid content.

[0293] The content of the compound represented by the formula (3) in the nonlinear optically active compound is preferably 0.0001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more, and is preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less, relative to the total content of the compound represented by the formula (1) and the compound represented by the formula (3). The content of 0.0001 mol% or more is preferable for reducing absorption loss, and 25 mol% or less is preferable for improving r33.

[0294] In one embodiment, the content of the compound represented by the formula (3) can be 0.0001 mol % or more and 25 mol % or less with respect to the total content of the compound represented by the formula (1) and the compound represented by the formula (3).

[0295] The content of other components in the composition is not particularly limited, but from the viewpoint of film uniformity, it is preferably 0.001 to 10 mass %, more preferably 0.01 to 5 mass %, and even more preferably 0.01 to 1 mass %, relative to 100 mass of the composition.

[0296] When the composition contains a polymer material, the content of the polymer material in the composition is not particularly limited, but from the viewpoint of coatability, it is preferably 0 to 99% by mass, more preferably 0 to 95% by mass, even more preferably 0 to 90% by mass, still more preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass, and particularly preferably 30 to 60% by mass, relative to the above-mentioned solid content.

[0297] The content of the organic solvent in the composition is not particularly limited, but from the viewpoint of film uniformity, it is preferably 60 to 99 mass % relative to 100 mass of the composition, and from the viewpoint of ensuring the stability of the composition, it is more preferably 70 to 99 mass %, and even more preferably 80 to 98 mass %.

[0298] <Nonlinear Optically Active Polymer Compound Containing a Group Obtained by Removing at Least One Hydrogen Atom from a Compound Represented by Formula (1)> One of the compositions according to an embodiment of the present invention comprises a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by Formula (1). Here, examples of the nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by Formula (1) include a polymer compound having, as a substituent of the polymer compound, a group obtained by removing at least one hydrogen atom from a compound represented by Formula (1), a polymer compound containing, as part of the main chain of the polymer compound, a group obtained by removing two hydrogen atoms from a compound represented by Formula (1), and a polymer compound in which two polymer compounds are bonded via a group obtained by removing two hydrogen atoms from a compound represented by Formula (1).

[0299] A group obtained by removing at least one hydrogen atom from a compound represented by formula (1) above is a group whose valency is the number of hydrogen atoms removed from the compound. For example, a group obtained by removing one hydrogen atom becomes a monovalent group, and groups obtained by removing two, three, and n hydrogen atoms become divalent, trivalent, and n-valent groups, respectively. For example, a group obtained by removing one hydrogen atom from a compound represented by formula (1) above is included as a substituent in a polymer compound. Furthermore, for example, a group obtained by removing two hydrogen atoms from a compound represented by formula (1) above can be included as a substituent in two separate polymer compounds. Alternatively, a structure sandwiched between structures in formula (1) from which hydrogen atoms have been removed can be included as part of the main chain of a polymer compound. In this case, the group obtained by removing two hydrogen atoms from a compound represented by formula (1) above can be included as the main chain of a polymer compound.

[0300] Furthermore, the polymer compound may contain multiple types of groups obtained by removing at least one hydrogen atom from the compound represented by formula (1). For example, in the polymer compound, some of the groups may be contained as substituents, and others may be contained as the main chain.

[0301] Preferred embodiments of the group obtained by removing at least one hydrogen atom from the compound represented by the above formula (1) are the same as those described for the compound represented by the formula (1).

[0302] <Repeating unit containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1)> A nonlinear optically active polymer compound containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) preferably has a repeating unit containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1). Specific examples of repeating units (Pa) containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) are shown below. The present invention is not limited to these.

[0303]

[0304]

[0305]

[0306]

[0307] <Optional Repeating Units> A nonlinear optically active polymer compound containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) may contain a repeating unit (R) in addition to the repeating unit containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1). Here, the repeating unit (R) does not include repeating units containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) or formula (3). By containing a repeating unit other than the repeating unit containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) or formula (3), the durability of the polymer compound is improved.

[0308] The repeating unit (R) is not particularly limited, and examples thereof include repeating units constituting poly(meth)acrylic acid esters (e.g., polymethyl methacrylate (PMMA), polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), polycarbonylaminoethyl methacrylate, etc.), polyamides, polyimides, polycarbonates, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyesters, polyolefins, polyphenylene sulfide, aromatic polyamines, polyamines, polyureas, silicone-based resins, epoxy-based resins, polyvinyl chloride, and fluoropolymers.

[0309] In particular, repeating units constituting at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimides, polycarbonates, polyalkyl-substituted maleimides, and polyaryl-substituted maleimides are more preferred because they are generally excellent as optical materials. From the viewpoint of compound stability, repeating units constituting polystyrene, polymethacrylic acid esters, polyalkyl-substituted maleimides, or polyaryl-substituted maleimides are most preferred. Preferred examples of polymethacrylic acid esters include polyadamantyl methacrylate (polyAdMA), polyalkyloxycarbonylaminoethyl methacrylate, polymethyl methacrylate (PMMA), and poly(cyclic or linear) alkyl methacrylates. Preferred examples of polyalkyl-substituted maleimides include polymethylmaleimide, polyethylmaleimide, and polypropylmaleimide. Preferred examples of polyaryl-substituted maleimides include polyphenylmaleimide, polytolylmaleimide, and polynaphthylmaleimide.

[0310] The nonlinear optically active polymer compound containing a group in which at least one hydrogen atom has been removed from the compound represented by formula (1) can contain, as the repeating unit (R), a repeating unit represented by the following formula (11):

[0311]

[0312] [In formula (11), R １１１ ~R １１６ each independently represents a hydrogen atom or a group selected from the hydrocarbon group group A which may have a substituent, １１１ and L １１２ each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group group A, which may have a substituent, an oxygen atom, a carbonyl group, a divalent aromatic group which may have a substituent, or a divalent heterocyclic group which may have a substituent; １１１ and Y １１２each independently represents a hydrogen atom, a group selected from the hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, or a heterocyclic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, or a silyl group which may have a substituent; １１３ ~R １１６ , L １１１ and L １１２ At least two of n may be bonded to form a ring; １１１ and n １１２ are each independently an integer of 0 to 5.

[0313] [R １１１ ~R １１６ ] R １１１ ~R １１６ each independently represents a hydrogen atom or an optionally substituted group selected from the hydrocarbon group group A. The optionally substituted group selected from the hydrocarbon group group A has the same meaning as described in the explanation of the above terms. From the viewpoint of the stability of the compound, R １１１ and R １１２ is preferably a hydrogen atom, and R １１３ ~R １１６ is preferably a hydrogen atom or an alkyl group as described above, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0314] [L １１１ , L １１２ ] L １１１ and L １１２ each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group group A, which may have a substituent, an oxygen atom, a carbonyl group, a divalent aromatic group which may have a substituent, or a divalent heterocyclic group which may have a substituent. The group selected from hydrocarbon group group A, which may have a substituent, the divalent aromatic group which may have a substituent, or the divalent heterocyclic group which may have a substituent are the same as those described in the explanation of the above terms. In terms of the stability of the compound, L １１１ and L １１２is preferably a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group group A, which may have a substituent, an oxygen atom, or a carbonyl group. １１３ ~R １１６ , L １１１ and L １１２ At least two of these may be bonded to form a ring.

[0315] [Y １１１ , Y １１２ ] Y １１１ and Y １１２ each independently represents a hydrogen atom, a group selected from the hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, or a heterocyclic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, or a silyl group which may have a substituent. The group selected from the hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, or a heterocyclic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, and a silyl group which may have a substituent are the same as those described in the explanation of the above terms. In terms of the stability of the compound, Y １１１ and Y １１２ is preferably a hydrogen atom, a group selected from hydrocarbon group group A which may have a substituent, or an aromatic group which may have a substituent, more preferably a hydrogen atom or a group selected from hydrocarbon group group A which may have a substituent, and particularly preferably a hydrogen atom.

[0316] [n １１１ , n １１２ ] n １１１ and n １１２ are each independently an integer of 0 to 5. In terms of the stability of the compound, n １１１ and n １１２ is preferably an integer of 0 to 2.

[0317] [Substituents] These R １１１ ~R １１６ , L １１１ , L １１２ , Y １１１ and Y １１２Unless otherwise specified, the substituents which may be possessed by each group are the same as those which may be possessed by each group described in the explanation of the above terms, and are preferably those which are included in the above substituent group W １ is a group selected from

[0318] Specific examples of the repeating unit (R) in this embodiment are shown below, but the present invention is not limited thereto.

[0319]

[0320]

[0321]

[0322] <Preferred specific examples of nonlinear optically active polymer compounds containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1)> Preferred specific examples are shown below. The present invention is not limited to these. PA represents a repeating unit (Pa) containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) described above, and PC represents the repeating unit (R) described above or a repeating unit (CL) containing a crosslinking group described below.

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334] (Exemplary Structure) Specific examples of the nonlinear optically active polymer compound containing a group in which at least one hydrogen atom has been removed from the compound represented by formula (1) in this embodiment are shown below, but the present invention is not limited to these.

[0335]

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349]

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368] <Nonlinear Optically Active Polymer Compound Containing a Group Obtained by Removing at Least One Hydrogen Atom from a Compound Represented by Formula (3)> One of the compositions according to an embodiment of the present invention comprises a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by Formula (3). Here, examples of the nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by Formula (3) include a polymer compound having, as a substituent of the polymer compound, a group obtained by removing at least one hydrogen atom from a compound represented by Formula (3), a polymer compound containing, as part of the main chain of the polymer compound, a group obtained by removing two hydrogen atoms from a compound represented by Formula (3), and a polymer compound in which two polymer compounds are bonded via a group obtained by removing two hydrogen atoms from a compound represented by Formula (3).

[0369] A group obtained by removing at least one hydrogen atom from a compound represented by formula (3) above is a group whose valency is the number of hydrogen atoms removed from the compound. For example, a group obtained by removing one hydrogen atom becomes a monovalent group, and groups obtained by removing two, three, and n hydrogen atoms become divalent, trivalent, and n-valent groups, respectively. For example, a group obtained by removing one hydrogen atom from a compound represented by formula (3) above is included as a substituent in a polymer compound. Furthermore, for example, a group obtained by removing two hydrogen atoms from a compound represented by formula (3) above can be included as a substituent in two separate polymer compounds. Alternatively, a structure sandwiched between structures in formula (3) from which hydrogen atoms have been removed can be included as part of the main chain of a polymer compound. In this case, a group obtained by removing two hydrogen atoms from a compound represented by formula (3) above can be included as the main chain of a polymer compound.

[0370] Furthermore, the polymer compound may contain multiple types of groups obtained by removing one hydrogen atom from the compound represented by formula (3). For example, in the polymer compound, some of the groups may be contained as substituents, and others may be contained as the main chain.

[0371] Preferred embodiments of the group obtained by removing at least one hydrogen atom from the compound represented by the above formula (3) are the same as those described for the compound represented by the formula (3).

[0372] <Repeating unit containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (3)> A nonlinear optically active polymer compound containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (3) as at least one selected from a substituent and a main chain preferably has a repeating unit containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (3). Specific examples of repeating units (Pb) containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (3) are shown below. The present invention is not limited to these.

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[0385] <Repeating units that may be included> A nonlinear optically active polymer compound containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (3) may contain the above-mentioned repeating unit (R) in addition to the repeating unit containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (3). Here, the repeating unit (R) does not include repeating units containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) or formula (3). It is preferable to contain a repeating unit other than the repeating unit containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) or formula (3) because this improves the durability of the polymer compound.

[0386] <Preferred specific examples of nonlinear optically active polymer compounds containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (3)> Preferred specific examples are shown below. The present invention is not limited to these. PB represents a repeating unit (Pb) containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (3) described above, and PC represents the repeating unit (R) described above or a repeating unit (CL) containing a crosslinking group described below.

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[0418] (Exemplary Structure) Specific examples of the nonlinear optically active polymer compound containing a group in which at least one hydrogen atom has been removed from the compound represented by formula (3) in this embodiment are shown below, but the present invention is not limited to these.

[0419]

[0420]

[0421]

[0422]

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[0452] <Nonlinear Optically Active Polymer Compound Comprising a Group in Which at Least One Hydrogen Atom Has Been Removed from a Compound Represented by Formula (1) and a Group in Which at Least One Hydrogen Atom Has Been Removed from a Compound Represented by Formula (3)> One of the polymer compounds according to an embodiment of the present invention comprises, as at least one selected from a substituent and a main chain, a group in Which at least one hydrogen atom has been removed from a compound represented by Formula (1) above and a group in Which at least one hydrogen atom has been removed from a compound represented by Formula (3) above. Here, examples of nonlinear optically active polymer compounds containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and a group obtained by removing at least one hydrogen atom from the compound represented by formula (3) as at least one selected from a substituent and a main chain include polymer compounds having a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and a group obtained by removing at least one hydrogen atom from the compound represented by formula (3) as the substituent of the polymer compound, polymer compounds containing a group obtained by removing two hydrogen atoms from the compound represented by formula (1) and a group obtained by removing two hydrogen atoms from the compound represented by formula (3) as part of the main chain of the polymer compound, and polymer compounds in which two polymer compounds are bonded via a group obtained by removing two hydrogen atoms from the compound represented by formula (1) and a group obtained by removing two hydrogen atoms from the compound represented by formula (3). Preferred embodiments of such polymer compounds will be described in detail below.

[0453] The group obtained by removing at least one hydrogen atom from the compound represented by formula (1) above and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) above are as described above in <Polymer compound containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1)> and <Polymer compound containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (3)>, respectively. It is preferable to have a repeating unit (Pa) containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and a repeating unit (Pb) containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (3), and specific examples of the repeating unit (Pa) and the repeating unit (Pb) are also as described above.

[0454] From the viewpoint of improving the reactivity when the resulting group is introduced into a polymer compound, the group obtained by removing at least one hydrogen atom from the compound represented by the above formula (1) is at least R １４ and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) is at least R ３４ Preferably, a hydrogen atom is removed from

[0455] (Content) In a polymer compound containing a group obtained by removing at least one hydrogen atom from a compound represented by the above formula (1) and a group obtained by removing at least one hydrogen atom from a compound represented by the above formula (3) as at least one selected from a substituent and a main chain, the content of the group obtained by removing at least one hydrogen atom from a compound represented by the above formula (3) is preferably 0.0001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more, and also preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less, relative to the total content of the group obtained by removing at least one hydrogen atom from a compound represented by the above formula (1) and the group obtained by removing at least one hydrogen atom from a compound represented by the above formula (3). The content of 0.0001 mol% or more is preferable for reducing absorption loss, and 25 mol% or less is preferable for improving r33. In one embodiment, the content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) can be 0.0001 mol % or more and 25 mol % or less with respect to the total content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3).

[0456] <Optional Repeating Units> One of the polymer compounds in this embodiment may contain the repeating unit (R) in addition to the repeating unit containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and the repeating unit containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (3). Here, the repeating unit (R) does not include repeating units containing a group obtained by removing at least one hydrogen atom from the compounds represented by formula (1) and formula (3). By containing a repeating unit other than the repeating units represented by formula (1) and formula (3), the durability of the polymer compound is improved.

[0457] <Preferred specific examples of nonlinear optically active polymer compounds containing a group obtained by removing at least one hydrogen atom from a compound represented by formula (1) and a group obtained by removing at least one hydrogen atom from a compound represented by formula (3)> Preferred specific examples are shown below. The present invention is not limited to these. PA represents a repeating unit (Pa) containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) above, PB represents a repeating unit (Pb) containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (3) above, and PC represents the repeating unit (R) above or a repeating unit (CL) containing a bridging group described below.

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[0489] (Exemplary Compounds) Specific examples of nonlinear optically active polymer compounds containing a group in which at least one hydrogen atom has been removed from a compound represented by formula (1) in this embodiment and a group in which at least one hydrogen atom has been removed from a compound represented by formula (3) are shown below. The present invention is not limited to these.

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[0525] <Composition containing a nonlinear optically active polymer compound> The composition according to the first embodiment of the present invention containing a nonlinear optically active polymer compound includes a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from the compound represented by formula (1), and a compound represented by formula (3). The composition may further contain an organic solvent.

[0526] A composition according to a second embodiment of the present invention containing a nonlinear optically active polymer compound includes a compound represented by formula (1) above and a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by formula (3) above. The composition may further contain an organic solvent.

[0527] A composition according to a third embodiment of the present invention, which includes a nonlinear optically active polymer compound, includes a nonlinear optically active polymer compound having, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by formula (1), and a nonlinear optically active polymer compound having, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by formula (3). The composition may further include an organic solvent.

[0528] A composition according to a fourth embodiment of the present invention, which includes a nonlinear optically active polymer compound, includes a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) above, and a group obtained by removing at least one hydrogen atom from the compound represented by formula (3) above, as at least one selected from a substituent and a main chain. The composition may further include an organic solvent.

[0529] Preferred embodiments of the composition according to the present invention containing a nonlinear optically active polymer compound will be described in detail below.

[0530] (Other Components) The composition according to the embodiment of the present invention, which contains a nonlinear optically active polymer compound, may contain the above-mentioned polymer compounds and / or other components. For example, the composition according to the embodiment of the present invention, which contains a nonlinear optically active polymer compound, may contain, as components other than the above-mentioned other components, 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile, 1-[3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene]malononitrile, malononitrile, etc. The above compounds may be contained in the composition as impurities generated during the manufacturing process.

[0531] (Content) There are no particular limitations on the content of each solid component (component other than the organic solvent contained in the composition) in the total solid content of the composition according to the first to fourth embodiments of the present invention, which contains a nonlinear optically active polymer compound, but the above-mentioned content is preferred.

[0532] In the composition according to the first embodiment of the present invention, which contains a nonlinear optically active polymer compound, the content of the compound represented by formula (3) is preferably 0.0001 mol% or more, more preferably 0.01 mol% or more, even more preferably 0.1 mol% or more, and preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less, relative to the total content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and the compound represented by formula (3). A content of 0.0001 mol% or more is preferred because absorption loss is reduced, and a content of 25 mol% or less is preferred because r33 is improved. In one embodiment, the content of the compound represented by formula (3) can be 0.0001 mol% or more and 25 mol% or less, relative to the total content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and the compound represented by formula (3).

[0533] In a composition according to a second embodiment of the present invention containing a nonlinear optically active polymer compound, the content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) is preferably 0.0001 mol% or more, more preferably 0.01 mol% or more, even more preferably 0.1 mol% or more, and preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less, relative to the total content of the compound represented by formula (1) and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3). A content of 0.0001 mol% or more is preferred for reducing absorption loss, and a content of 25 mol% or less is preferred for improving r33. In one embodiment, the content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) can be 0.0001 mol% or more and 25 mol% or less, relative to the total content of the compound represented by formula (1) and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3).

[0534] In the composition according to the third embodiment of the present invention, which contains a nonlinear optically active polymer compound, the content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) is preferably 0.0001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more, and is preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less, relative to the total content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3). The content of 0.0001 mol% or more is preferable for reducing absorption loss, and 25 mol% or less is preferable for improving r33. In one embodiment, the content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) above can be 0.0001 mol % or more and 25 mol % or less with respect to the total content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) above and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) above.

[0535] In the composition according to the fourth embodiment of the present invention, which contains a nonlinear optically active polymer compound, the content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) is preferably 0.0001 mol% or more, more preferably 0.01 mol% or more, and even more preferably 0.1 mol% or more, and is preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less, relative to the total content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3). A content of 0.0001 mol% or more is preferable for reducing absorption loss, and a content of 25 mol% or less is preferable for improving r33. In one embodiment, the content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) above can be 0.0001 mol % or more and 25 mol % or less with respect to the total content of the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) above and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) above.

[0536] When at least one of a group in which at least one hydrogen atom has been removed from a compound represented by formula (1) and a group in which at least one hydrogen atom has been removed from a compound represented by formula (3) is included in the content, the content is １ The content can be determined by comparing the integral value of a specific hydrogen atom obtained from H-NMR measurement. The content can also be determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer. Specifically, the content can be determined by dividing the mass absorption coefficient of the compound represented by formula (1) and / or formula (3) by the mass absorption coefficient of a nonlinear optically active polymer compound containing at least one of a group in which at least one hydrogen atom has been removed from the compound represented by formula (1) and a group in which at least one hydrogen atom has been removed from the compound represented by formula (3). Here, the mass absorption coefficient refers to the absorbance of a nonlinear optical material solution at a unit weight concentration.

[0537] [Method for producing a composition] There are no particular limitations on the method for producing a composition, as long as it includes a step of dissolving the nonlinear optical material described above in the organic solvent described above. One embodiment includes a method for producing a composition that includes a step of mixing the polymer material described above with the organic solvent described above, and heating and stirring to dissolve, a step of mixing the solution with the nonlinear optically active compound described above, and stirring to dissolve, and a step of filtering the solution. Another embodiment includes a method for producing a composition that includes a step of mixing the nonlinear optically active polymer compound described above with the organic solvent described above, and stirring to dissolve, and a step of filtering the solution.

[0538] [Uses of the composition] There are no particular limitations on the uses of the composition, but it is generally used to form a nonlinear optical material into a film or thin film. The nonlinear optical material formed into a film or thin film can be used in a nonlinear optical element. That is, the composition can be used as an ink for forming a nonlinear optical element.

[0539] The method for forming a film or thin film from the composition is not particularly limited, and examples thereof include known techniques such as injection molding, press molding, soft lithography, and wet coating. Among these, wet coating methods such as spin coating, blade coating, dip coating, and inkjet coating are preferred from the viewpoints of ease of use of the production equipment, mass productivity, and film quality (uniformity of film thickness, few defects such as bubbles, etc.). One example is a method in which a composition in which the nonlinear optically active compound and the polymer material are dissolved in the organic solvent is coated on a substrate and dried. Here, "drying" refers to, for example, a process in which the substrate is placed on a heating device such as a hot plate and heated to dry, or a process in which the coated substrate is placed in a chamber and evacuated to dry, or a combination of both processes. Another example is a method in which a composition in which the nonlinear optically active polymer compound is dissolved in the organic solvent is coated on a substrate and dried under vacuum.

[0540] <Nonlinear Optical Element> A nonlinear optical element according to an embodiment of the present invention comprises a film formed from the above composition or the above polymer compound.

[0541] A nonlinear optical element according to a first embodiment of the present invention comprises a film formed from a composition containing a compound represented by formula (1) above and a compound represented by formula (3). A nonlinear optical element according to a second embodiment of the present invention comprises a film formed from a composition containing a polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from the compound represented by formula (1). A nonlinear optical element according to a third embodiment of the present invention comprises a film formed from a composition containing a compound represented by formula (1) above and a polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from the compound represented by formula (3).

[0542] A nonlinear optical element according to a fourth embodiment of the present invention comprises a film formed from a composition containing a polymer compound including, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from the compound represented by formula (1), and a polymer compound including, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from the compound represented by formula (3). A nonlinear optical element according to a fifth embodiment of the present invention comprises a film formed from a composition containing a polymer compound including, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) and a group obtained by removing at least one hydrogen atom from the compound represented by formula (3).

[0543] A nonlinear optical element according to a sixth embodiment of the present invention comprises a film formed from a polymer compound containing, as at least one selected from a substituent and a main chain, a group in which at least one hydrogen atom has been removed from a compound represented by the above formula (1) and a group in which at least one hydrogen atom has been removed from a compound represented by the above formula (3).

[0544] The nonlinear optical element is not particularly limited as long as it uses the above-mentioned composition or nonlinear optically active polymer compound and operates based on the nonlinear optical effect, and examples thereof include wavelength conversion elements, photorefractive elements, and electro-optical elements. Among these, nonlinear optical elements that operate based on the electro-optic effect are preferred, and more specifically, electro-optical elements such as optical switches, optical modulators, and phase shifters are preferred. In one embodiment, the nonlinear optical element can be an optical modulator equipped with the above-mentioned nonlinear optical element.

[0545] The electro-optical element is preferably formed by forming a film made of the above-mentioned composition or nonlinear optically active polymer compound on a substrate and sandwiching it between a pair of electrodes for inputting electrical signals.

[0546] There are no particular limitations on the film thickness of the film formed from the above-mentioned composition or polymer compound, but in order to make the nonlinear effect effective, the film thickness is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 0.8 μm or more, and in order not to inhibit the light waveguiding, the film thickness is preferably 50 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

[0547] Examples of materials that can be used to form such substrates include metals such as aluminum, gold, iron, nickel, chromium, and titanium; semiconductors such as silicon, titanium oxide, zinc oxide, and gallium arsenide; glass; and plastics such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polysulfone, polyether ketone, and polyimide.

[0548] A conductive film may be formed on the surface of the substrate. Examples of materials for such a conductive film include metals such as aluminum, gold, nickel, chromium, and titanium; conductive oxides such as tin oxide, indium oxide, ITO (tin oxide-indium oxide composite oxide), and IZO (indium oxide-zinc oxide composite oxide); and conductive polymers such as polythiophene, polyaniline, polyparaphenylene vinylene, and polyacetylene. The conductive film is formed using a known dry film formation method such as vapor deposition or sputtering, or a known wet film formation method such as dip coating or electrolytic deposition, and may be patterned as needed. The conductive substrate, or the conductive film formed on the substrate as described above, is used as an electrode (hereinafter also referred to as the "lower electrode") during poling or during operation as a device.

[0549] On the surface of the substrate, if necessary, an adhesive layer for improving the adhesion between the film formed thereon and the substrate, a leveling layer for smoothing the unevenness of the substrate surface, or some intermediate layer that provides these functions all at once may be formed.The material for forming such a film is not particularly limited, and known materials such as acrylic resin, methacrylic resin, amide resin, vinyl chloride resin, vinyl acetate resin, phenolic resin, urethane resin, vinyl alcohol resin, acetal resin, etc. and their copolymers; zirconium chelate compound, titanium chelate compound, crosslinked material of silane coupling agent, etc. and their co-crosslinked material can be used.

[0550] The electro-optical element is preferably formed to include a waveguide structure, and it is particularly preferable that the film formed from the above-described composition or polymer compound is contained in the core layer of the waveguide.

[0551] A clad layer (hereinafter also referred to as a "lower clad layer") may be formed between the substrate and the film formed from the composition or the core layer containing the polymer compound. This lower clad layer may be any material as long as it has a lower refractive index than the core layer and is not affected during the formation of the core layer. Preferred materials for forming the lower clad layer include, for example, UV-curable or thermosetting resins such as acrylic, epoxy, oxetane, thiirane, and silicone resins; polyimide; and glass.

[0552] After forming the core layer using the above-mentioned composition or polymer compound, a clad layer (hereinafter also referred to as "upper clad layer") may be further formed on top of it in the same manner as the lower clad layer, thereby forming a slab waveguide having a structure of substrate / lower clad layer / core layer / upper clad layer.

[0553] After forming the core layer, the core layer can be patterned by a known method using semiconductor process technology such as reactive ion etching (RIE), photolithography, electron beam lithography, etc. to form a channel waveguide or a ridge waveguide. Alternatively, a channel waveguide can be formed by patterning and irradiating part of the core layer with UV light, electron beam, etc., to change the refractive index of the irradiated part.

[0554] A basic electro-optical element can be formed by forming an electrode (hereinafter also referred to as an "upper electrode") for applying an input electrical signal to the surface of the upper clad layer in a desired region of the upper clad layer.

[0555] When a channel waveguide or a ridge waveguide is formed as described above, the core layer pattern can be configured to have a known device structure such as a linear type, a Y-branch type, a directional coupler type, or a Mach-Zehnder type, and can be applied to known optical information communication devices such as optical switches, optical modulators, phase shifters, etc. One example of the application to an optical information communication device is an optical modulator equipped with a nonlinear optical element that operates based on the above-mentioned electro-optic effect.

[0556] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0557] <Synthesis of Dye, Sub Dye, and EO Polymer> Each dye, sub dye, and EO polymer was synthesized by the following method.

[0558] <Synthesis of Secondary Dye 1> The following secondary dye 1 was synthesized in the same manner as compound 10b described in Journal of Polymer Science Part A: Polymer Chemistry, 2010, 49, 47-54.

[0559]

[0560] <Synthesis of Dye 1>

[0561]

[0562] In a 500 mL three-neck flask, under a nitrogen stream, ethanol (200 mL) was added to a THF (100 mL) solution of secondary dye 1 (12.0 g, 23.6 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (8.20 g, 28.6 mmol), and the mixture was stirred at room temperature for 18 hours. The solution was then concentrated under reduced pressure and purified by silica gel chromatography to obtain dye 1 (14.5 g, yield 76.2%).

[0563] The results of NMR measurement of Dye 1 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.79 (d, J = 15.1Hz, 1H), 7.46 (m, 12H), 7.29 (t, J = 4.6Hz, 1H), 7.15 (d , J=15.6Hz, 1H), 6.93(d, J=4.1Hz, 1H), 6.56(d, J=15.1Hz, 1H), 6.34(d d, J=9.1, 2.3Hz, 1H), 6.19 (d, J=2.3Hz, 1H), 5.18 (s, 2H), 3.73 (t, J=5. 7Hz, 2H), 3.50 (t, J=5.7Hz, 2H), 3.04 (s, 3H), 0.87 (s, 9H), 0.07 (s, 6H) Since the peak of the aldehyde group of the raw material, secondary dye 1, was below the detection limit, it was confirmed that the content of secondary dye 1 contained in dye 1 was less than 0.0001 mol %.

[0564] <Synthesis of Compound 1>

[0565]

[0566] Under a nitrogen stream, 4-bromosalicylaldehyde (20.1 g, 0.10 mol), potassium carbonate (27.6 g, 0.20 mol), and DMF (200 mL) were added to a 500 mL three-neck flask and stirred. After cooling to 0°C in an ice bath, benzyl bromide (20.5 g, 0.12 mol) was added dropwise and stirred at 0°C for 2 hours. After the reaction, the temperature was raised to room temperature, and the reaction solution was poured into water (400 mL) and extracted with ethyl acetate (400 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 1 (7.60 g, yield 77.6%).

[0567] <Synthesis of Compound 2>

[0568]

[0569] Under a nitrogen stream, compound 1 (16.3 g, 56.1 mmol), diethyl-2-thienylmethylphosphonate (15.8 g, 67.3 mmol), and THF (163 mL) were mixed in a 500 mL three-neck flask and cooled to 0°C in an ice bath. Potassium tert-butoxide (6.92 g, 61.7 mmol) was slowly added to the reaction solution, and the mixture was then warmed to room temperature and stirred for 4 hours. After the reaction, the reaction solution was poured into water (100 mL) and extracted with ethyl acetate (400 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2 (17.4 g, yield 83.7%).

[0570] <Synthesis of Compound 3>

[0571]

[0572] Under a nitrogen stream, potassium hydroxide (17.8 g, 0.28 mol) was slowly added to a solution of dihexylamine (25.0 g, 0.14 mol) in DMSO (540 mL) in a 500 mL three-neck flask, and the mixture was stirred at room temperature for 30 minutes. Then, 1-bromo-3,5-dimethylbenzene (50.0 g, 0.28 mol) was added dropwise. After the addition was complete, the mixture was heated to 50°C and stirred for 9 hours. After the reaction, the reaction solution was poured into water (500 mL) and extracted with ethyl acetate (800 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 3 (25.2 g, yield 64.4%).

[0573] <Synthesis of Compound 4>

[0574]

[0575] Under a nitrogen stream, compound 3 (22.2 g, 76.7 mmol) and 4 M aqueous hydrogen chloride solution (114 mL) were mixed in a 500 mL three-neck flask, cooled to -5°C, and then an aqueous solution (3 mL) of sodium nitrite (5.82 g, 84.4 mmol) was added dropwise with stirring. After the dropwise addition, the mixture was stirred at -5°C to 0°C for 1 hour. Then, 8 M aqueous hydrogen chloride solution (205 mL) was added to the reaction solution, and zinc powder (22.1 g, 337 mmol) was slowly added at 0°C. The reaction solution was warmed to 25°C and stirred for 4 hours. After stirring, the mixture was neutralized with sodium hydroxide and extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 4 (15.1 g, yield 64.5%).

[0576] <Synthesis of Compound 5>

[0577]

[0578] Under a nitrogen atmosphere, a 500 mL three-neck flask was charged with a solution of compound 2 (19.3 g, 51.9 mmol) and compound 4 (15.8 g, 51.9 mmol) in toluene (259 mL), and sodium tert-butoxide (12.5 g, 130 mmol), palladium acetate (116 mg, 0.52 mmol), and 2-2'bis(diphenylphosphino-1-1')-binaphthyl (BINAP) (646 mg, 1.04 mmol) were added, followed by stirring at 100°C for 6 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 5 (24.0 g, yield 73.1%).

[0579] <Synthesis of Compound 6>

[0580]

[0581] In a 1 L flask, 2-(N-methylanilino)ethanol (80.0 g, 0.53 mol), pyridine (400 mL), and 1,4-dioxane (400 mL) were mixed and cooled to 0°C, and then iodine (201 g, 0.80 mol) was added. The reaction solution was then heated to 35°C and stirred for 7 hours. After completion of the reaction, the reaction solution was diluted with DCM (800 mL) and washed with a saturated aqueous solution of sodium thiosulfate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 6 (74.0 g, yield 50.4%).

[0582] <Synthesis of Compound 7>

[0583]

[0584] Under a nitrogen stream, a solution of compound 6 (20.0 g, 72.2 mmol) in DMF (200 mL) in a 500 mL flask was cooled to 0°C, and then tert-butyldimethylchlorosilane (TBDMSCl) (11.90 g, 79.4 mmol) was added. The reaction solution was then heated to 25°C and stirred for 2 hours. After the reaction, the reaction solution was poured into water (200 mL) and extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 7 (22.9 g, yield 81.1%).

[0585] <Synthesis of Compound 8>

[0586]

[0587] In a 100 mL three-neck flask, a solution of compound 5 (595 mg, 1.0 mmol) and compound 7 (470 mg, 1.2 mmol) in toluene (6.70 mL) was added with sodium tert-butoxide (240 g, 2.5 mmol), Pd ２ (dba) ３ (18.0mg, 0.02mmol), tert-Bu ３ PHBF ４(23 mg, 0.039 mmol) was added, and the mixture was stirred at 100° C. for 8 hours. After the reaction, water (10 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (20 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 8 (586 mg, yield 63.6%).

[0588] <Synthesis of secondary dye 2>

[0589]

[0590] Under a nitrogen stream, a solution of compound 8 (2.10 g, 2.4 mmol) in THF (21 mL) in a 100 mL three-neck flask was cooled to -78°C, and n-BuLi (1.6 M in hexane, 1.70 mL) was added. After stirring at -78°C for 1 hour, DMF (0.74 mL) diluted with THF (0.8 mL) was added, and the mixture was heated to 0°C and stirred for 3 hours. After the reaction, water (50 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain secondary dye 2 (1.56 g, yield 73.1%).

[0591] The results of NMR measurement of Sub Dye 2 are shown below. １ H-NMR (400MHz, DMSO-d6) δ9.80 (s, 1H), 7.89 (d, 1H), 7.19-7.40 (m, 9H) , 6.29 (d, 2H), 6.60 (d, 2H), 6.38 (s, 2H), 6.31 (d, 1H), 6.18 (dd, 1H), 4.9 6 (s, 2H), 3.72 (t, 1H), 3.41 (t, 2H), 3.25 (m, 4H), 2.90 (s, 3H), 1.87 (s, 6H), 1.52 (m, 4H), 1.29 (m, 12H), 0.86 (t, 6H), 0.80 (s, 9H), -0.04 (s, 6H)

[0592] <Synthesis of Dye 2>

[0593]

[0594] In a 200 mL three-neck flask, under a nitrogen stream, ethanol (50 mL) and piperidine (0.29 g, 0.34 mmol) were added to a THF (25 mL) solution of secondary dye 2 (1.00 g, 1.13 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (0.43 g, 1.35 mmol), and the mixture was heated to 45°C. The mixture was then stirred at 45°C for 10 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain dye 2 (0.17 g, yield 12.7%).

[0595] The results of NMR measurement of Dye 2 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ 7.77 (d, 1H), 7.53 (m, 6H), 7.28-7.36 (m, 7H), 7.13 (d, 1H), 6.94 (m, 3H), 6.56 (m, 3H), 6.35 (m, 4H), 4.99 (s, 2H), 3.77 (t, 2H), 3.42 (t, 3H), 3.25 (t, 4H), 2.96 (s, 3H), 1.94 (s, 4H), 1.58 (m, 4H), 1.34 (m, 12H), 0.87-0.93 (m, 15H), 0.02 (s, 6H). Since the peak of the aldehyde group of the raw material secondary dye 2 was below the detection limit, it was confirmed that the content of secondary dye 2 in dye 2 was less than 0.0001 mol%.

[0596] <Synthesis of Compound 9>

[0597]

[0598] Under a nitrogen atmosphere, a 500 mL three-neck flask was charged with a solution of compound 2 (17.0 g, 45.8 mmol) and 2,4,6-trimethylaniline (9.30 g, 68.7 mmol) in toluene (229 mL), and sodium tert-butoxide (11.0 g, 114.5 mmol), palladium acetate (103 mg, 0.46 mmol), and 2-2'bis(diphenylphosphino-1-1')-binaphthyl (BINAP) (570 mg, 0.92 mmol) were added, followed by stirring at 100°C for 10 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 9 (13.7 g, yield 70.3%).

[0599] <Synthesis of Compound 10>

[0600]

[0601] In a 500 mL three-neck flask, a solution of compound 9 (11.9 g, 28.0 mmol) and compound 7 (13.1 g, 33.6 mmol) in toluene (186 mL) was added with sodium tert-butoxide (6.72 g, 69.9 mmol), Pd ２ (dba) ３ (512mg, 0.56mmol), tert-Bu ３ PHBF ４ After adding (649 mg, 2.24 mmol), the mixture was stirred at 100°C for 6.5 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 10 (12.1 g, yield 62.9%).

[0602] <Synthesis of Compound 11>

[0603]

[0604] Under a nitrogen stream, a solution of compound 10 (12.0 g, 17.4 mmol) in THF (120 mL) in a 500 mL three-neck flask was cooled to -78 °C, and n-BuLi (1.6 M in hexane, 12 mL) was added. After stirring at -78 °C for 1 hour, DMF (5.4 mL) diluted with THF (5.0 mL) was added, and the mixture was heated to 0 °C and stirred for 3 hours. After the reaction, water (50 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 11 (9.09 g, yield 72.8%).

[0605] <Synthesis of Compound 12>

[0606]

[0607] Under a nitrogen stream, compound 11 (10.0 g, 14.0 mmol), diethyl-2-thienylmethylphosphonate (3.92 g, 16.8 mmol), and THF (100 mL) were mixed in a 500 mL three-neck flask and cooled to 0°C in an ice bath. Potassium tert-butoxide (2.03 g, 18.2 mmol) was slowly added to the reaction solution, and the mixture was warmed to room temperature and stirred for 4.5 hours. After the reaction, the reaction solution was poured into water (100 mL) and extracted with DCM (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 12 (7.96 g, yield 71.6%).

[0608] <Synthesis of secondary dye 3>

[0609]

[0610] Under a nitrogen stream, a solution of compound 12 (7.53 g, 9.44 mmol) in THF (75 mL) in a 100 mL three-neck flask was cooled to -78°C, and n-BuLi (1.6 M in hexane, 6.5 mL) was added. After stirring at -78°C for 1 hour, DMF (2.8 mL) diluted with THF (3.0 mL) was added, and the mixture was heated to -30°C and stirred for 3 hours. After the reaction, water (50 mL) was added to the reaction solution heated to 0°C, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain secondary dye 3 (6.39 g, yield 82.0%).

[0611] The results of NMR measurement of Sub Dye 3 are shown below. １ H-NMR (400MHz, DMSO-d6) δ9.85 (s, 1H), 7.94 (d, 1H), 7.43 (d, 1H), 7. 34-7.40 (m, 5H), 7.10-7.26 (m, 6H), 6.99 (d, 1H), 6.95 (s, 2H), 6.78 (d , 2H), 6.60 (d, 2H), 6.29 (d, 1H), 6.14 (dd, 1H), 3.73 (t, 2H), 3.42 (t, 2 H), 2.90 (s, 3H), 2.29 (s, 3H), 1.89 (s, 6H), 0.81 (s, 9H), -0.04 (s, 6H)

[0612] <Synthesis of Dye 3>

[0613]

[0614] In a 200 mL three-neck flask, under a nitrogen stream, ethanol (100 mL) was added to a THF (50 mL) solution of secondary dye 3 (5.00 g, 60.6 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (2.48 g, 7.88 mmol), and the mixture was stirred for 16 hours at 25° C. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain dye 3 (4.50 g, yield 66.2%).

[0615] The results of NMR measurement of Dye 3 are shown below. １ H-NMR (400MHz, CDCl ３) δ7.78 (d, 1H), 7.49-7.56 (m, 5H), 7.28-7.38 (m, 7H), 7.26 (d, 1H), 7.11 (d, 1H), 7.03 (d, 1H), 6.85-6.91 (m, 6H), 6.62 (d, 1H), 6. 56 (d, 2H), 6.35 (m, 2H), 4.95 (s, 2H), 3.77 (t, 2H), 3.43 (s, 2H), 2.95 (s, 3H), 2.33 (s, 3H), 1.95 (s, 6H), 0.87 (s, 9H), 0.02 (s, 6H) Since the peak of the aldehyde group of the raw material secondary dye 3 was below the detection limit, it was confirmed that the content of secondary dye 3 contained in dye 3 was less than 0.0001 mol %.

[0616] <Synthesis of Dye 4>

[0617]

[0618] In a 300 mL flask, a solution of dye 1 (5.00 g, 60.6 mmol) in THF (150 mL) was cooled to 0°C, and 4 M aqueous hydrogen chloride solution (45 mL) was added dropwise. After the addition, the temperature was raised to 25°C and stirred for 2 hours. After the reaction was completed, water (200 mL) was added, neutralized with potassium carbonate, and extracted with DCM (200 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting solid was redissolved in DCM (50 mL), and hexane (100 mL) was added. The resulting precipitate was collected by filtration. The filtered product was washed with hexane (50 mL) and dried to obtain dye 4 (3.80 g, yield 88.6%).

[0619] The results of NMR measurement of Dye 4 are shown below. １ H-NMR (400MHz, CDCl ３) δ 7.78 (d, 1H), 7.46-7.58 (m, 8H), 7.35-7.44 (m, 4H), 7.15 (d, 1H), 6.92 (d, 1H), 6.55 (d, 1H), 6.39 (d, 1H), 6.28 (s, 1H), 5.20 (s, 2H), 3.78 (t, 2H), 3.53 (t, 2H), 3.05 (s, 3H). The peaks of the aldehyde groups of the raw material dye 1 precursor (secondary dye 1) and secondary dye 4, in which the tert-butyldimethylsilyl group of secondary dye 1 was substituted with hydrogen, were below the detection limit, confirming that the content of secondary dyes 1 and 4 in dye 4 was less than 0.0001 mol%.

[0620] <Synthesis of Dye 5>

[0621]

[0622] In a 300 mL flask, a solution of dye 2 (2.20 g, 60.6 mmol) in THF (50 mL) was cooled to 0° C., and 4 M aqueous hydrogen chloride solution (14 mL) was added dropwise. After the addition, the temperature was raised to 25° C. and stirred for 2 hours. After the reaction was completed, water (100 mL) was added, neutralized with potassium carbonate, and extracted with DCM (200 mL). The DCM solution was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain dye 5 (3.20 g, yield 89.1%).

[0623] The results of NMR measurement of Dye 5 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.77 (d, 1H), 7.50-7.58 (m, 6H), 7.28-7.38 (m, 7H), 7.15 (d, 1H), 6.95 (m, 3H), 6.69 (d, 2H), 6.56 (d, 1H)), 6.34.3 8 (m, 4H), 5.00 (s, 2H), 3.81 (t, 2H), 3.43 (s, 2H), 3.25 (m, 4H), 2.93 (s, 3H), 1.94 (s, 6H), 1.34 (s, 12H), 0.91 (s, 6H)

[0624] <Synthesis of Dye 6>

[0625]

[0626] In a 300 mL flask, a solution of dye 3 (4.00 g, 35.6 mmol) in THF (90 mL) was cooled to 0°C, and 4 M aqueous hydrogen chloride solution (27 mL) was added dropwise. After the addition, the temperature was raised to 25°C and stirred for 2 hours. After the reaction was completed, water (100 mL) was added, neutralized with potassium carbonate, and extracted with DCM (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain dye 6 (1.60 g, yield 80.5%).

[0627] The results of NMR measurement of Dye 6 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.78 (d, 1H), 7.47-7.58 (m, 5H), 7.30-7.40 (m, 7H), 7.08-7.24 (m, 2H), 7.04 (m, 2H), 6.86-6.91 (m, 6H), 6. 61-6.69 (m, 3H), 6.38 (m, 2H), 4.97 (m, 2H), 3.81 (t, 2H), 3.40 (t, 2H), 2.92 (s, 3H), 2.37 (s, 3H), 1.95 (s, 6H)

[0628] <Synthesis of secondary dye 4>

[0629]

[0630] In a 100 mL flask, a solution of secondary dye 1 (1.00 g, 1.97 mmol) in THF (10 mL) was stirred at 25°C, and a 1 M THF solution (2.2 mL) of tetrabutylammonium fluoride (TBAF) was added dropwise. After the addition, the mixture was stirred at 25°C for 3 hours. After the reaction was completed, water (50 mL) was added, and the mixture was extracted with DCM (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain secondary dye 4 (722 mg, yield 88.8%).

[0631] The results of NMR measurement of Sub Dye 4 are shown below. １ H-NMR (400MHz, CDCl ３) δ9.79 (s, 1H), 7.60 (d, 1H), 7.33-7.48 (m, 7H), 7.14 (d, 1H), 6.99 (d, 1H), 6. 39 (dd, 1H), 6.30 (d, 1H), 3.78 (dd, 2H), 3.49 (t, 2H), 3.01 (t, 3H), 1.60 (t, 1H)

[0632] <Synthesis of Compound 13>

[0633]

[0634] Under a nitrogen stream, compound 1 (50.0 g, 0.17 mol) and isophorone (24.9 g, 0.18 mol) were dissolved in methanol (172 mL) in a 500 mL flask, and 4 M aqueous sodium hydroxide solution (86 mL, 0.34 mol) was added. The mixture was then stirred at reflux temperature for 3 hours. After completion of the reaction, the reaction solution was poured into water (100 mL) and extracted with DCM (200 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting solid was washed with hexane to obtain compound 13 (63.0 g, yield 88.8%).

[0635] <Synthesis of Compound 14>

[0636]

[0637] Under a nitrogen stream, sodium hydride (60%, liquid paraffin dispersion) (520 mg, 13.0 mmol) and tetrahydrofuran (10 mL) were mixed in a 100 mL flask and cooled to 0 °C. A solution of diethyl cyanomethylphosphonate (2.3 g, 13 mmol) in tetrahydrofuran (10 mL) was then slowly added, and the mixture was warmed to room temperature and stirred for 1 hour. A solution of compound 13 (4.11 g, 10.0 mmol) in tetrahydrofuran (10 mL) was then slowly added, and the mixture was stirred at room temperature for 30 minutes, followed by stirring at reflux temperature for 4 hours. After completion of the reaction, the reaction solution was poured into water (30 mL) and extracted with DCM (100 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting solid was washed with hexane to obtain compound 14 (3.5 g, yield 80.6%).

[0638] <Synthesis of Compound 15>

[0639]

[0640] Under a nitrogen stream, 2-(N-methylanilino)ethanol (151.2 g, 1.00 mol) was mixed with N,N-dimethylformamide (1.51 L) in a 3 L flask and cooled to 0°C. Then, a solution of N-bromosuccinimide (186.9 g, 1.10 mol) in N,N-dimethylformamide (560 mL) was slowly added, and the mixture was stirred at 0°C for 3 hours. After completion of the reaction, the reaction solution was poured into water (2 L) and extracted with DCM (1 L). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 15 (214.4 g, yield 93.2%).

[0641] <Synthesis of Compound 16>

[0642]

[0643] Under a nitrogen stream, compound 15 (214.4 g, 0.93 mol) was mixed with N,N-dimethylformamide (2.14 L) in a 3 L flask, and imidazole (126.9 g, 1.86 mol) was added. After the solution was cooled to 0°C, tert-butyldimethylchlorosilane (154.5 g, 1.02 mol) was slowly added. The reaction solution was warmed to room temperature and stirred at room temperature for 4 hours. After completion of the reaction, the reaction solution was poured into water (2 L) and extracted with DCM (1 L). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 16 (266.1 g, yield 82.5%).

[0644] <Synthesis of Compound 17>

[0645]

[0646] In a 200 mL flask, compound 16 (3.44 g, 10.0 mmol) and 2,4,6-trimethylaniline (1.62 g, 12.0 mmol) were dissolved in toluene (50 mL), and the solution was bubbled with argon at room temperature for 20 minutes. ２ (dba) ３ (183mg, 0.2mmol), tert-Bu ３ PHBF ４(232 mg, 0.8 mmol) and tert-BuONa (2.40 g, 25.0 mmol) were added, and the reaction solution was heated to 80°C. The reaction solution was then stirred at 80°C for 8 hours. The mixture was then air-cooled to room temperature, and water (50 mL) was added to the reaction solution, followed by extraction with DCM (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 17 (3.31 g, yield 81.1%).

[0647] <Synthesis of Secondary Dye 5>

[0648]

[0649] In a 50 mL flask, compound 17 (399 mg, 1.0 mmol) and compound 14 (478 mg, 1.1 mmol) were dissolved in toluene (10 mL), and the solution was bubbled with argon at room temperature for 20 minutes. ２ (dba) ３ (18mg, 0.02mmol), tert-Bu ３ PHBF ４ (23 mg, 0.08 mmol) and tert-BuONa (240 mg, 2.50 mmol) were added, and the reaction solution was heated to reflux. The reaction solution was then stirred at reflux for 10 hours. After that, it was air-cooled to room temperature, and water (20 mL) was added to the reaction solution, followed by extraction with DCM (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain secondary dye 5 (449 mg, yield 66.4%).

[0650] The results of NMR measurement of Sub Dye 5 are shown below. １H-NMR (400MHz, d6-DMSO) δ7.30-7.50 (m, 5H), 7.20-7.30 (m, 2H), 6.90-7.10 (m, 4H), 6.73-6.86 (m, 2H), 6.58-6.62 (m, 2H), 6.41 (d, 1H), 6.25 (d, 1H), 6.13 (m, 1H) ), 5.32 (d, 1H), 4.95 (s, 2H), 3.72 (t, 2H), 3.41 (t, 2H), 2.90 (s, 3H), 2.37 (s, 1H ), 2.20-2.30 (m, 6H), 1.87 (d, 6H), 0.94-0.97 (d, 7H), 0.81 (s, 9H), -0.04 (s, 6H)

[0651] <Synthesis of secondary dye 6>

[0652]

[0653] Under a nitrogen stream, secondary dye 5 (16.0 g, 21.3 mmol) was dissolved in toluene (426 mL) in a 1 L flask and cooled to -78°C. A 1.0 M solution of diisobutylaluminum hydride in hexane (26.4 mL, 26.4 mmol) was then added, and the mixture was stirred at -78°C for 4 hours. Water (100 mL) was then added to the reaction solution, which was then warmed to room temperature and extracted with DCM (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain secondary dye 6 (8.15 g, yield 50.7%).

[0654] The NMR measurement results of Sub Dye 6 are shown below. １ H-NMR (400MHz, d6-DMSO) δ10.16-9.96 (d, 1H), 7.40-7.05 (m, 8H), 6.96-6. 87 (m, 3H), 6.76 (d, 2H), 6.59 (d, 2H), 6.30 (d, 2H), 6.17-6.13 (m, 1H), 5.82 ( d, 1H), 5.63 (d, 1H), 4.95 (s, 2H), 3.72 (t, 2H), 3.41 (t, 2H), 2.90 (s, 3H), 2. 25-2.30 (m, 6H), 1.87 (s, 6H), 0.94-0.97 (m, 7H), 0.81 (s, 9H), -0.04 (s, 6H)

[0655] <Synthesis of Dye 7>

[0656]

[0657] In a 200 mL three-neck flask, under a nitrogen stream, ethanol (50 mL) was added to a solution of secondary dye 6 (1.00 g, 1.32 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (0.46 g, 1.46 mmol) in tetrahydrofuran (25 mL), and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain dye 7 (1.39 g, yield 44.5%).

[0658] The NMR measurement results of Dye 7 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.77 (d, 1H), 7.53 (m, 6H), 7.28-7.36 (m, 7H), 7.13 (d, 1H), 6.94 (m, 3H), 6.56 (m, 3H), 6.35 (m, 4H), 4.99 (s, 2H), 3.77 ( t, 2H), 3.42 (t, 3H), 3.25 (t, 4H), 2.96 (s, 3H), 1.94 (s, 4H), 1.58 (m, 4H), 1.34 (m, 12H), 0.87-0.93 (m, 15H), 0.02 (s, 6H)

[0659] <Synthesis of secondary dye 7>

[0660]

[0661] In a 100 mL flask, a solution of secondary dye 6 (1.00 g, 1.32 mmmol) in THF (33 mL) was cooled to 0°C, and 4 M aqueous hydrogen chloride solution (11 mL) was added dropwise. After the addition, the temperature was raised to 25°C and stirred for 2 hours. After the reaction was completed, water (100 mL) was added, neutralized with potassium carbonate, and extracted with DCM (200 mL). The organic layer was dried over sodium sulfate and filtered, and the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain secondary dye 7 (220 mg, yield 25.9%).

[0662] The NMR measurement results of Sub Dye 7 are shown below. １ H-NMR (400MHz, CDCl ３) δ10.19-10.25 (d, 1H), 7.29-7.34 (m, 7H), 7.11-7.19 (m, 1H), 6.81-6.95 (m, 5H), 6.69 (d, 2H), 6.22-6.38 (m, 3H), 5.67-5.90 (d , 1H), 4.95 (s, 2H), 4.11 (q, 1H), 3.78-3.80 (m, 2H), 3.40-3.43 (m, 2H), 2.91 (s, 3H), 2.26-2.40 (m, 6H), 1.26 (t, 2H), 1.02 (s, 6H)

[0663] <Synthesis of Dye 8>

[0664]

[0665] In a 200 mL three-neck flask, under a nitrogen stream, ethanol (30 mL) was added to a solution of secondary dye 7 (0.22 g, 0.34 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (0.12 g, 0.38 mmol) in tetrahydrofuran (15 mL), and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain dye 8 (160 mg, yield 49.7%).

[0666] The NMR measurement results of Dye 8 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.50-7.52 (m, 5H), 7.33-7.37 (m, 6H), 6.91-6.92 (m, 5H), 6.70 (d, 2H), 6.27-6.39 (m, 4H), 4.96 ( s, 2H), 3.80 (t, 2H), 3.43 (t, 2H), 2.95 (s, 3H), 2.40 (s, 2H), 2.33 (s, 3H), 1.91 (s, 6H), 1.00 (s, 3H), 0.95 (s, 2H)

[0667] <Synthesis of secondary dye 8>

[0668]

[0669] Under a nitrogen stream, a 50 mL flask was charged with a solution of diethyl cyanomethylphosphonate (675 mg, 3.81 mmol) in tetrahydrofuran (7.6 mL). The mixture was then cooled to 0°C, followed by the addition of a hexane solution of n-butyllithium (1.6 M, 1.75 mL, 2.80 mmol). The reaction solution was then warmed to room temperature and stirred at room temperature for 1 hour. After cooling to 0°C again, a solution of secondary dye 4 (1.0 g, 2.54 mmol) in tetrahydrofuran (5.1 mL) was added. After the addition, the mixture was stirred at room temperature for 30 minutes and then at reflux temperature for 5 hours. After the reaction was complete, the mixture was air-cooled to room temperature, water (30 mL) was added, and the mixture was extracted with DCM (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain secondary dye 8 (750 mg, yield 70.9%).

[0670] The NMR measurement results of Sub Dye 8 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.49-7.27 (m, 9H), 7.06-7.11 (m, 2H), 6.85 (d, 1H), 6.38 (dd, 1H), 6.30 (d, 1H), 5 .48 (d, 2H), 5.15 (s, 2H), 3.78 (t, 2H), 3.47 (t, 2H), 3.00 (s, 3H), 1.58-1.62 (m, 7H)

[0671] <Synthesis of secondary dye 9>

[0672]

[0673] Under a nitrogen atmosphere, a solution of compound 11 (10.0 g, 14.0 mmol) in THF (174 mL) was cooled to 0°C in a 500 mL three-neck flask, and hydrochloric acid (4.0 M in water, 105 mL) was added. After the addition, the temperature was raised to room temperature and stirred for 1.5 hours. The reaction solution was neutralized with sodium bicarbonate and extracted with dichloromethane. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain secondary dye 9 (7.26 g, yield 86.4%).

[0674] <Synthesis of Dye 9>

[0675]

[0676] In a 300 mL three-neck flask, under a nitrogen stream, ethanol (40 mL) was added to a THF (20 mL) solution of secondary dye 9 (0.50 g, 0.83 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (0.34 g, 10.8 mmol), and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain dye 9 (390 mg, yield 52.2%).

[0677] The results of NMR measurement of Dye 9 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ 7.76 (d, 1H), 7.48-7.57 (m, 5H), 7.36-7.23 (m, 8H), 7.16 (d, 1H), 6.91-6.96 (m, 5H), 6.68 (d, 2H), 6.58 (d, 1H), 6.37 (dd, 1H), 6.30 (d, 1H), 4.98 (s, 2H), 3.81 (t, 2H), 3.43 (t, 2H), 2.94 (s, 3H), 2.34 (s, 3H), 1.95 (s, 6H). Since the peak of the aldehyde group of the raw material secondary dye 9 was below the detection limit, it was confirmed that the content of secondary dye 9 in dye 9 was less than 0.0001 mol%.

[0678] <Synthesis of Compound 18>

[0679]

[0680] Under a nitrogen atmosphere, a solution of secondary dye 9 (5.0 g, 8.3 mmol) in THF (83 mL) was cooled to 0°C in a 300 mL three-neck flask, and imidazole (904 mg, 13.3 mmol) and triphenylphosphine (2.9 g, 11.2 mmol) were added. Then, iodine (2.74 g, 10.8 mmol) in THF (9 mL) was slowly added. After the addition, the mixture was warmed to room temperature and stirred for 1 hour. After the reaction, saturated aqueous sodium thiosulfate solution (50 mL) was added to the reaction solution, which was then extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 18 (5.03 g, 85.1% yield).

[0681] The results of NMR measurement of compound 18 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ9.81 (s, 1H), 7.91 (d, 1H), 7.44-7.22 (m, 9H), 6.97 (s, 2H), 6.81 (d, 2H), 6.62 (d, 2H), 6.29 (d, 1H), 6.16 (dd, 2H), 4.99 (s, 2H), 3.65 (t, 2H), 3.30 (t, 2H), 2.90 (s, 3H), 2.29 (s, 3H), 1.89 (s, 6H)

[0682] <Synthesis of Compound 19>

[0683]

[0684] Under a nitrogen stream, a 200 mL three-neck flask was cooled to -5°C with a solution of 2,4,6-trimethylaniline (2.7 g, 20 mmol) in THF (40 mL), and sodium hydride (60%, dispersed in liquid paraffin) (800 mg, 20 mmol) was slowly added. After the addition, the mixture was stirred for 1 hour while warming to room temperature. The reaction solution was cooled again to -5°C, and a solution of (2-bromoethoxy)-tert-butylmethylsilane (2.39 g, 10 mmol) in THF (5 mL) was added. After the addition, the mixture was stirred for 1.5 hours while warming to room temperature. After the reaction, water (30 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 19 (1.56 g, yield 53.4%).

[0685] <Synthesis of Compound 20>

[0686]

[0687] In a 10 L flask, a solution of isophorone oxide (493.9 g, 3.2 mol) in ethylene glycol (4.84 L, 86.5 mol) was bubbled with nitrogen at room temperature for 30 minutes. Then, 48% aqueous sodium hydroxide solution (400.3 g, 4.8 mol) was slowly added over 18 minutes. After the addition, the mixture was stirred for 2 hours while the temperature was raised from room temperature to 50°C. The reaction solution was then heated to 80°C and stirred for 3.5 hours. After the reaction was completed, the mixture was extracted with dichloromethane and washed with deionized water and saturated aqueous sodium chloride solution to obtain compound 20 (707 g, yield 85.5%).

[0688] <Synthesis of Compound 21>

[0689]

[0690] In a 20 L flask, a solution of compound 1 (701.5 g, 2.41 mol) and compound 20 (684.2 g, 2.65 mol) in methanol (8.03 L) was bubbled with nitrogen at room temperature for 20 minutes. The mixture was then cooled to -15°C, and a solution of sodium methoxide in methanol (5 M, 1.06 L, 5.3 mol) was slowly added. After the addition, the mixture was heated to reflux and stirred for 5 hours. After completion of the reaction, the reaction solution was cooled to -10°C, and deionized water (1 L) was slowly added. After evaporation, the methanol was removed, followed by extraction with ethyl acetate, and the solvent was removed using an evaporator. The resulting solid was suspended and washed with methyl tert-butyl ether and filtered to obtain the first crystals. The filtrate was evaporated to dryness using an evaporator, purified by silica gel chromatography, suspended and washed with methyl tert-butyl ether, and the second crystals were collected by filtration. The first and second crystals were combined and dried under reduced pressure to obtain Compound 21 (700.9 g, yield 61.7%).

[0691] <Synthesis of Compound 22>

[0692]

[0693] Under an argon atmosphere, in a 10 L flask, sodium tert-butoxide (185.5 g, 1.93 mol) in THF (1.49 L) was cooled to -20°C, and a solution of diethyl cyanomethylsulfonate (342.0 g, 1.93 mol) in THF (1.49 L) was slowly added. The mixture was stirred for 1 hour while warming to 0°C. The reaction solution was then cooled to -15°C, and compound 21 (700 g, 1.49 mol) in THF (1.49 L) was added. After the addition, the reaction solution was stirred for 1 hour while warming to 20°C, and then further stirred at reflux temperature for 4 hours. After completion of the reaction, water was added to the reaction solution, which was then extracted with ethyl acetate, and the organic layer was evaporated to dryness. The resulting solid was azeotroped with methanol (1.1 L), and the residue was redissolved in methanol (1.12 L) and allowed to stand overnight. The resulting solid was collected by filtration, rinsed with methanol (560 mL), and then dried in vacuo to obtain Compound 22 (360.5 g, yield 48.9%).

[0694] <Synthesis of Compound 23>

[0695]

[0696] Under a nitrogen stream, 3,4-dihydro-2H-pyran (46.8 g, 556 mmol) and pyridinium p-toluenesulfonate (PPTS) (11.2 g, 44.5 mmol) were added to a dichloromethane (742 mL) solution of compound 22 (110 g, 223 mmol) in a 3 L flask, and the mixture was stirred at room temperature for 1 hour and then at 40°C for 3.5 hours. After completion of the reaction, water (500 mL) was added to the reaction solution, which was then extracted with dichloromethane. The organic layer was evaporated to dryness, and the resulting solid was suspended and washed with hexane to obtain compound 23 (110.1 g, yield 85.5%).

[0697] <Synthesis of Compound 24>

[0698]

[0699] In a 3 L flask, compound 19 (65.1 g, 222 mmol) was added to a solution of compound 23 (107 g, 185 mmol) in toluene (1 L), and the mixture was subjected to argon bubbling at room temperature for 20 minutes. Then, sodium tert-butoxide (24.9 g, 259 mmol) and Pd２ (dba) ３ A solution of 2-methyl-2-propanol (1.69 g, 1.85 mmol) and XPhos (3.53 g, 7.4 mmol) in toluene (88.2 mL) was added. After the addition, the reaction solution was stirred at 90°C for 5 hours. After the reaction was completed, water (500 mL) was added to the reaction solution, and the mixture was extracted with dichloromethane. The organic layer was evaporated to dryness and purified by silica gel column chromatography to obtain compound 24 (96.6 g, yield 62.3%).

[0700] <Synthesis of Compound 25>

[0701]

[0702] Under a nitrogen stream, a solution of compound 24 (95.5 g, 113 mmol) in toluene (2.27 L) in a 5 L flask was cooled to -72°C, and diisobutylaluminum hydride (1 M, hexane solution) (249 mL, 249 mmol) was slowly added. After the addition, the mixture was stirred at -75°C to -66°C for 2 hours, and then stirred at -40°C for an additional 1 hour. The mixture was then recooled to -75°C, and diisobutylaluminum hydride (1 M, hexane solution) (22.7 mL, 22.7 mmol) was slowly added. After the addition, the mixture was stirred at -40°C for 2 hours. After completion of the reaction, water (1 L) was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was evaporated to dryness and purified by silica gel column chromatography to obtain compound 25 (63.3 g, yield 70.4%).

[0703] <Synthesis of Secondary Dye 10>

[0704]

[0705] In a 3 L flask, pyridinium p-toluenesulfonate (2.99 g, 11.9 mmol) was added to a THF (630 mL) / methanol (630 mL) mixed solution of compound 25 (63.0 g, 79.3 mmol), and the mixture was stirred at 60 °C for 3.5 hours. After completion of the reaction, water (1 L) was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride solution and evaporated to dryness using an evaporator. The resulting solid was dispersed in acetonitrile (488 mL), and the solid was completely dissolved by heating to 60 °C. The mixture was then concentrated using an evaporator until the acetonitrile was reduced to approximately half its original volume, and allowed to stand at room temperature for 1 hour under a nitrogen stream. The mixture was then cooled to 0 °C and allowed to stand for 3 hours. The resulting crystals were collected by filtration and rinsed with ice-cooled acetonitrile (163 mL) to obtain the first crystals. The filtrate was concentrated, acetonitrile (377 mL) was added, and the mixture was heated to 60 °C to completely dissolve the solids. The acetonitrile was then concentrated to approximately one-third its original volume using an evaporator and allowed to stand at room temperature for 1 hour under a nitrogen stream. The mixture was then cooled to 0°C and allowed to stand for 9 hours. The resulting crystals were collected by filtration and rinsed with ice-cold acetonitrile (88 mL) to obtain a second crystal. The first and second crystals were combined and redissolved in acetonitrile, filtered, and the filtrate was concentrated and vacuum-dried to obtain secondary dye 10 (22.6 g, yield 40.1%).

[0706] The results of NMR measurement of Sub Dye 10 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ10.07 (s, 1H), 7.10-7.45 (m, 12H), 6.30 (d, 1H), 4.97 (s, 1H), 3.78-3.90 (m, 4H), 3.68 (dt, 4 H), 2.74 (s, 2H), 2.42 (s, 2H), 2.34 (s, 3H), 1.95 (s, 6H), 1.07 (s, 6H), 0.87 (s, 9H), 0.03 (s, 6H)

[0707] <Synthesis of Dye 10>

[0708]

[0709] Under a nitrogen stream, secondary dye 10 (0.1 g, 0.141 mmol) and 2-[3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene]malononitrile (28.1 mg, 0.141 mmol) were dissolved in anhydrous THF (5 mL) in a 25 mL three-neck flask, and then anhydrous ethanol (2.5 mL) was added. Ammonium acetate (10.9 mg, 0.141 mmol) was added to the reaction solution, and the mixture was stirred at 60°C for 2 hours. After the reaction was completed, the solvent was removed by evaporation, and the residue was purified by silica gel column chromatography and dried under reduced pressure to obtain dye 10 (100 mg, yield 79.7%).

[0710] The results of NMR measurement of Dye 10 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ8.03 (dd, 1H), 7.11-7.52 (m, 7H), 6.93 (d, 2H), 6.92 (d, 1H), 6.30 (d, 2H), 3.87 (dt, 4H), 3.76 (t , 2H), 3.62 (t, 2H), 2.71 (d, 4H), 2.34 (s, 6H), 1.68 (s, 6H), 1.05 (s, 6H), 0.87 (s, 9H), 0.03 (s, 6H)

[0711] <Synthesis of Base Polymer 1>

[0712]

[0713] Methyl methacrylate (MMA) (12.8 g, 127.8 mmol), 1-adamantyl methacrylate (28.2 g, 128.0 mmol), and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (16.1 g, 64.1 mmol) were dissolved in deoxygenated toluene (110 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (171 mg, 0.69 mmol) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then heated to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (120 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with hexane (120 mL) and dried in vacuo to obtain base polymer 1 (35.0 g, yield 61%).

[0714] The molecular weight of the obtained base polymer 1 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 114,000 and the number average molecular weight Mn was 34,000.

[0715] <Synthesis of Base Polymer 2>

[0716]

[0717] Methyl methacrylate (MMA) (1.59 g, 15.9 mmol), 1-adamantyl methacrylate (3.51 g, 15.9 mmol), and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (2.0 g, 7.95 mmol) were dissolved in deoxygenated toluene (24.6 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (20 mg, 0.08 mmol) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then heated to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (120 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with hexane (120 mL) and dried in vacuo to obtain base polymer 2 (3.76 g, yield 50.6%).

[0718] The molecular weight of the obtained base polymer 2 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 58,900 and the number average molecular weight Mn was 28,500.

[0719] <Synthesis of Monomer 1>

[0720]

[0721] Under a nitrogen stream, 1-[2-(methacryloyloxy)ethyl] succinate (10.0 g, 43.4 mmol), N-hydroxysuccinimide (5.5 g, 11.0 mmol), and 4-dimethylaminopyridine (DMAP) (531 mg, 1 mmol) were dissolved in THF (100 mL). After cooling to 0°C, a THF (20 mL) solution of N,N'-dicyclohexylcarbodiimide (DCC) (9.86 g, 11.0 mmol) was added. After addition, the mixture was stirred at room temperature for 3 hours. The solution was then concentrated under reduced pressure and purified by silica gel chromatography to obtain Monomer 1 (12.0 g, yield 79.8%).

[0722] <Synthesis of Base Polymer 3>

[0723]

[0724] Methyl methacrylate (MMA) (2.89 g, 28.8 mmol), 1-adamantyl methacrylate (6.36 g, 28.8 mmol), and Monomer 1 (5.0 g, 14.4 mmol) were dissolved in deoxygenated toluene (32 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (36 mg, 0.14 mmol) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then heated to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (120 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with hexane (120 mL). The collected product was redissolved in THF (28 mL) and added dropwise to methanol (280 mL). The resulting solid was collected by filtration. The filtered product was redissolved in THF (28 mL) and added dropwise to hexane (280 mL). The resulting solid was filtered and dried under vacuum at 50° C. for 5 hours to obtain base polymer 3 (5.52 g, yield 39.1%).

[0725] The molecular weight of the obtained base polymer 3 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 152,000 and the number average molecular weight Mn was 54,000.

[0726] <Synthesis of Base Polymer 4>

[0727]

[0728] Styrene (625 mg, 6.00 mmol), 2-ethynyl-9,9-dimethyl-9H-fluorene (2.20 g, 10.0 mmol), and 2,5-dioxo-pyrrolidinyl-4-ethynylbenzoate (981 mg, 4.00 mmol) were added to a flask and purged with nitrogen. The mixture was then dissolved in deoxygenated DMF (4.0 mL) and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (20 mg, 0.07 mmol) was added. Further deoxygenated DMF (4.0 mL) was added, and after purging with nitrogen, the reaction solution was heated to 60°C and stirred for 6 hours. The temperature was then raised to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and diluted with THF (38 mL). The diluted solution was added dropwise to methanol (380 mL), and the resulting solid was collected by filtration. The filtered solid was rinsed with methanol (200 mL) and dried under vacuum. The dried solid was redissolved in THF (36 mL) and filtered. The filtrate was added dropwise to methanol (360 mL), and the resulting solid was collected by filtration. The filtered solid was rinsed with methanol (200 mL) and dried under vacuum to obtain base polymer 4 (2.38 g, yield 61.8%).

[0729] The molecular weight of the obtained base polymer 4 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 37,500 and the number average molecular weight Mn was 19,000.

[0730] <Synthesis of Base Polymer 5>

[0731]

[0732] Styrene (978 mg, 9.40 mmol), N-ethylmaleimide (705 mg, 5.64 mmol), and N-succinimidyl 3-maleimidopropionate (1.0 g, 3.76 mmol) were added to a flask and purged with nitrogen. The mixture was then dissolved in deoxygenated DMF (4.0 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (19 mg, 0.07 mmol) was added. Further deoxygenated DMF (4.0 mL) was added, and after purging with nitrogen, the reaction solution was heated to 60°C and stirred for 6 hours. The temperature was then raised to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and diluted with THF (200 mL). The diluted solution was added dropwise to methanol (400 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with methanol (200 mL) and dried in vacuo. The dried solid was redissolved in THF (50 mL) and filtered. The filtrate was added dropwise to methanol (450 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with methanol (200 mL) and dried under vacuum to obtain base polymer 5 (1.72 g, yield 63.2%).

[0733] The molecular weight of the obtained base polymer 5 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 74,000 and the number average molecular weight Mn was 24,000.

[0734] <Synthesis of Base Polymer 6′>

[0735]

[0736] Azobisisobutyronitrile (AIBN) (1.22 g, 0.37 mol) was added to a flask and purged with nitrogen. The mixture was then dissolved in deoxygenated THF (90 mL), and styrene (30.0 g, 0.26 mol) and 4-acetoxystyrene (18.0 g, 0.11 mol) were added. The reaction solution was heated to 65°C and stirred for 8 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (1.8 L). The mixture was stirred at room temperature for 15 minutes, and the resulting solid was collected by filtration. The collected solid was dried in vacuum at 50°C for 4 hours to obtain base polymer 6' (25.5 g).

[0737] The molecular weight of the obtained base polymer 6′ was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mm ID×150 mm L, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 19,400 and the number average molecular weight Mn was 12,600.

[0738] <Synthesis of Base Polymer 6>

[0739]

[0740] Under a nitrogen stream, concentrated hydrochloric acid (2.8 mL, 0.11 mol) was added to a solution of base polymer 6' (25.5 g, 0.21 mol) in ethanol (181 mL) in a 500 mL three-neck flask. After the addition, the temperature was raised to 90°C and stirred for 3.5 hours. After the reaction, the reaction solution was air-cooled to room temperature and poured into water (200 mL). The resulting solid was collected by filtration and vacuum-dried at 50°C for 7 hours to obtain base polymer 6 (19.5 g).

[0741] The molecular weight of the obtained base polymer 6 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 17,200 and the number average molecular weight Mn was 10,600.

[0742] <Synthesis of Secondary Dye-Containing Methacrylate Monomer>

[0743]

[0744] Secondary dye 4 (394 mg) was dissolved in dichloromethane (3.9 mL) under a nitrogen stream and cooled to 0°C, after which 2-isocyanatoethyl methacrylate (155 μL) and triethylamine (14 μL) were added. After stirring at room temperature for 2 hours, the temperature was raised to 45°C and stirring was continued for an additional 2 hours. After air-cooling to room temperature, the reaction solution was evaporated to dryness and purified by silica gel column chromatography to obtain a secondary dye-containing methacrylate monomer (530 mg, yield 96.6%).

[0745] <Synthesis of Base Polymer 7>

[0746]

[0747] Styrene (3.00 g, 25.4 mmol) and 1-adamantyl methacrylate (3.18 g, 25.4 mmol) were dissolved in anhydrous DMF (78 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (67 mg, 0.20 mmol) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then heated to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (120 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with hexane (120 mL) and dried in vacuo to obtain base polymer 7 (3.2 g, yield 52%). The molecular weight of the obtained base polymer 7 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). Two peaks were observed, the first of which had a weight average molecular weight Mw of 114,000 and a number average molecular weight Mn of 34,000, and the second of which had a weight average molecular weight Mw of 501,000.

[0748] <Synthesis of Compound 26>

[0749]

[0750] In a 1 L three-neck flask, 3-bromophenol (23.6 g, 137 mmol) and potassium carbonate (37.8 g, 275 mmol) were added to a solution of 7-bromobicyclo[4.2.0]octa-1,3,5-triene (25.0 g, 137 mmol) in dehydrated DMF (250 mL), and the reaction solution was subjected to nitrogen bubbling for 20 minutes. The reaction solution was then heated to 70°C and stirred for 7.5 hours. After the reaction, the reaction solution was air-cooled to room temperature and poured into water (400 mL). After extraction with dichloromethane (100 mL x 3), the organic layer was washed with water (100 mL) and brine (100 mL). The organic layer was dried over sodium sulfate and filtered, and the solution was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound 26 (20.2 g, 53.8%).

[0751] <Synthesis of Monomer 2>

[0752]

[0753] A 500 mL three-neck flask was charged with a solution of compound 26 (20.2 g, 137 mmol) and 3-vinylphenylboronic acid (20.3 g, 137 mmol) in THF (184 mL) and a 2 M aqueous potassium phosphate solution (91.8 mL, 343 mmol), and nitrogen was bubbled through for 20 minutes. ３ ) ４ (2.55 g, 2.2 mmol) was added to the reaction solution and stirred at 70°C for 6 hours. After the reaction, the reaction solution was air-cooled to room temperature and water (100 mL) was added. After extraction with dichloromethane (100 mL x 3), the organic layer was washed with water (100 mL) and brine (100 mL). The organic layer was dried over sodium sulfate and filtered. The solution was concentrated under reduced pressure and purified by silica gel column chromatography and reverse flow column chromatography to obtain Monomer 2 (10.2 g, 46.4%).

[0754] <Synthesis of Base Polymer 8>

[0755]

[0756] Styrene (1.35 mg, 13.0 mmol), N-ethylmaleimide (1.22 g, 9.73 mmol), Monomer 2 (968 mg, 3.24 mmol), and N-succinimidyl 3-maleimidopropionate (2.0 g, 6.49 mmol) were added to a flask and purged with nitrogen. The mixture was then dissolved in deoxygenated DMF (46.6 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (32.2 mg, 0.25 mmol) was added. After purging with nitrogen, the reaction solution was heated to 60°C and stirred for 6 hours. The temperature was then raised to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was cooled to 0°C and diluted with THF (11 mL). The diluted solution was added dropwise to methanol (500 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with methanol (250 mL) and dried in vacuo. The dried solid was redissolved in THF (50 mL) and filtered. The filtrate was added dropwise to methanol (450 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with methanol (250 mL) and dried under vacuum to obtain base polymer 8 (4.67 g, yield 83.3%).

[0757] The molecular weight of the obtained base polymer 8 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultiporeHZ-M (4.6 mmID×150 mmL, 4 μm, S)×2, TSKguard column SuperMP(HZ)-M, developing solvent: THF, column temperature: 40° C.). The weight average molecular weight Mw was 138,000 and the number average molecular weight Mn was 30,540.

[0758] <Synthesis of EO Polymer 1> EO Polymer 1, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 4, was synthesized by the following steps.

[0759]

[0760] Base polymer 1 (439 mg) and dye 4 (100 mg) were dissolved in anhydrous 1,4-dioxane (0.57 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (44 μL) was added. The mixture was stirred for 3 hours in an oil bath at 110 °C. Subsequently, anhydrous methanol (0.57 mL) and dibutyltin dilaurate (DBTDL) (44 μL) were added, and the mixture was stirred for 2 hours in an oil bath at 110 °C. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 80 °C to obtain EO polymer 1 (425 mg). The glass transition temperature (Tg) was measured using a Shimadzu Corporation DSC-60A Plus differential scanning calorimeter (DSC). The Tg was defined as the temperature at which the gradient of the rising part of the endothermic process of the baseline shift in the DSC curve, which shows the change in the calorific value when the temperature was increased at a rate of 10°C / min, intersects with the baseline. This measurement revealed that the Tg of EO Polymer 1 was 149°C.

[0761] The content of the group obtained by removing one hydrogen atom from dye 4 contained in EO polymer 1 is １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ (δ=5.20 ppm) and H ｂ , H ｃ , H ｄ , and H ｅ The content of secondary dyes 1 and 4 in EO polymer 1 was confirmed to be less than 0.01 mol % by mass, as calculated from the ratio of the total integrated values ​​of the peaks (δ = 3.87 - 4.40 ppm) of secondary dyes 1 and 4. The peaks of the aldehyde groups in the precursor of dye 4 (secondary dye 1), which is a raw material, and secondary dye 4 in which the tert-butyldimethylsilyl group in secondary dye 1 was substituted with hydrogen were below the detection limit.

[0762] The molecular weight of the obtained EO polymer 1 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel guard column Super AW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guard column Super AW-H, developing solvent: 0.5 mass % lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight average molecular weight Mw was 420,000 and the number average molecular weight Mn was 110,000.

[0763]

[0764] <Synthesis of EO Polymer 2'> EO Polymer 2', a polymer compound containing a group in which one hydrogen atom has been removed from Secondary Dye 4, was synthesized by the following steps.

[0765]

[0766] Base polymer 1 (668 mg) and secondary dye 4 (200 mg) were dissolved in anhydrous 1,4-dioxane (21.6 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (72 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (0.47 mL) and dibutyltin dilaurate (DBTDL) (72 μL) were added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 80°C to obtain EO polymer 2' (640 mg).

[0767] The content of the group obtained by removing one hydrogen atom from the secondary dye 4 contained in the EO polymer 2′ is １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ (δ=5.16 ppm) and H ｂ , H ｃ , H ｄ , and H ｅThe content was calculated from the ratio of the total integrated value of (δ=3.87-4.40 ppm) and was found to be 21 mass %.

[0768]

[0769] <Synthesis of EO Polymer 2> EO Polymer 2, a polymer compound containing groups in which one hydrogen atom has been removed from each of Dye 4 and Sub Dye 4, was synthesized by the following steps.

[0770]

[0771] In a 200 mL three-neck flask, under a nitrogen stream, ethanol (20 mL) was added to a THF (10 mL) solution of EO polymer 2' (0.35 g) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (140 mg, 0.45 mmol), and the mixture was stirred for 5 hours. After completion of the reaction, the solution was added dropwise to methanol, and the resulting solid was collected by filtration. The collected material was dried under vacuum at 80°C to obtain EO polymer 2 (340 mg).

[0772] The content of the group obtained by removing one hydrogen atom from each of dye 4 and sub-dye 4 contained in EO polymer 2 is １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ and H ｂ (δ=5.03-5.30 ppm) integral value and H ｃ , H ｄ , H ｅ , H ｆ , H ｇ , and H ｈ The integral of the sum of (δ=3.87-4.40 ppm), H ｉ When calculated from the ratio of the integrated values ​​of (δ = 9.76 ppm), the content of the group in which one hydrogen atom has been removed from dye 4 was 32 mass %, and the content of the group in which one hydrogen atom has been removed from secondary dye 4 relative to the total content of the groups in which one hydrogen atom has been removed from dye 4 and secondary dye 4 was 5.60 mol %.

[0773]

[0774] <Synthesis of EO Polymer 3> EO Polymer 3, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 5, was synthesized by the following steps.

[0775]

[0776] Under a nitrogen stream, base polymer 1 (437 mg) and dye 5 (100 mg) were dissolved in anhydrous 1,4-dioxane (12.9 mL), dibutyltin dilaurate (DBTDL) (43 μL) was added, and the mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (0.69 mL) and dibutyltin dilaurate (DBTDL) (43 μL) were added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 80°C to obtain EO polymer 3 (420 mg).

[0777] The content of the group obtained by removing one hydrogen atom from dye 5 contained in EO polymer 3 is １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ (δ=4.98 ppm) and H ｂ , H ｃ , H ｄ , and H ｅ The content of secondary dye 2 in EO polymer 3 was confirmed to be less than 0.01 mol % by mass, as calculated from the ratio of the total integrated value of the secondary dye 2 in EO polymer 3 (δ = 3.87 - 4.40 ppm). The peaks of the aldehyde group in the precursor of dye 5 (secondary dye 2), which was a raw material, and the compound in which the tert-butyldimethylsilyl group of secondary dye 2 was substituted with hydrogen were below the detection limit.

[0778]

[0779] <Synthesis of EO Polymer 4> EO Polymer 4, which is a polymer compound containing groups in which one hydrogen atom has been removed from each of Dye 5 and Sub Dye 4, was synthesized by the following steps.

[0780]

[0781] Base polymer 1 (437 mg), dye 5 (100 mg), and secondary dye 4 (2 mg) were dissolved in anhydrous 1,4-dioxane (12.9 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (43 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (0.69 mL) and dibutyltin dilaurate (DBTDL) (43 μL) were added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 80°C to obtain EO polymer 4 (380 mg). The glass transition temperature (Tg) of EO Polymer 4 was measured in the same manner as for EO Polymer 1, and the Tg of EO Polymer 4 was found to be 150°C.

[0782] The content of the group obtained by removing one hydrogen atom from each of the dye 5 and the sub-dye 4 contained in the EO polymer 4 is １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ (δ=4.98 ppm) and H ｂ (δ=5.18 ppm) and H ｃ , H ｄ , H ｅ , H ｆ , H ｇ , and H ｈ The integral of the sum of (δ=3.87-4.40 ppm), H ｉ When calculated from the ratio of the integrated values ​​of (δ = 9.76 ppm), the content of the group in which one hydrogen atom has been removed from dye 5 was 26 mass %, and the content of the group in which one hydrogen atom has been removed from secondary dye 4 relative to the total content of the groups in which one hydrogen atom has been removed from dye 5 and secondary dye 4 was 6.72 mol %.

[0783] The molecular weight of the obtained EO polymer 4 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel guard column Super AW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guard column Super AW-H, developing solvent: 0.5 mass % lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight average molecular weight Mw was 470,000 and the number average molecular weight Mn was 89,000.

[0784]

[0785] <Synthesis of EO Polymer 5> EO Polymer 5, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 6, was synthesized by the following steps.

[0786]

[0787] Under a nitrogen stream, base polymer 1 (437 mg) and dye 6 (100 mg) were dissolved in anhydrous 1,4-dioxane (13.0 mL), dibutyltin dilaurate (DBTDL) (43 μL) was added, and the mixture was stirred in an oil bath at 110 °C for 3 hours. Subsequently, anhydrous methanol (0.68 mL) and dibutyltin dilaurate (DBTDL) (43 μL) were added, and the mixture was stirred in an oil bath at 110 °C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 80 °C to obtain EO polymer 5 (410 mg). The glass transition temperature (Tg) of EO Polymer 5 was measured using a Shimadzu Corporation differential scanning calorimeter (DSC) DSC-60A Plus in the same manner as for Glass EO Polymer 1, and the Tg of EO Polymer 5 was found to be 149°C.

[0788] The content of the group obtained by removing one hydrogen atom from dye 6 contained in EO polymer 5 is １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ (δ=4.93 ppm) and H ｂ, H ｃ , H ｄ , and H ｅ The content was calculated from the ratio of the total integrated value of (δ=3.87-4.40 ppm) and was found to be 18% by mass.

[0789] The peaks of the aldehyde groups of the raw material precursor of dye 6 (secondary dye 3) and the compound in which the tert-butyldimethylsilyl group of secondary dye 3 was substituted with hydrogen were below the detection limit, so it was confirmed that the content of secondary dye 3 and the compound in which the tert-butyldimethylsilyl group of secondary dye 3 was substituted with hydrogen in EO polymer 5 was less than 0.01 mol%.

[0790] The molecular weight of the obtained EO polymer 5 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel guard column Super AW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guard column Super AW-H, developing solvent: 0.5 mass % lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight average molecular weight Mw was 94,000 and the number average molecular weight Mn was 35,000.

[0791]

[0792] <Synthesis of EO Polymer 6> EO Polymer 6, a polymer compound containing groups in which one hydrogen atom has been removed from each of Dye 6 and Sub Dye 4, was synthesized by the following steps.

[0793]

[0794] Base polymer 2 (330 mg), dye 6 (200 mg), and secondary dye 4 (2 mg) were dissolved in anhydrous 1,4-dioxane (10.2 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (34 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (0.275 mL) and dibutyltin dilaurate (DBTDL) (34 μL) were added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 80°C to obtain EO polymer 6 (400 mg).

[0795] The content of the group obtained by removing one hydrogen atom from each of the dye 6 and the sub-dye 4 contained in the EO polymer 6 is expressed as follows: １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ (δ=4.93 ppm) and H ｂ (δ=5.18 ppm) and H ｃ , H ｄ , H ｅ , H ｆ , H ｇ , and H ｈ The integral of the sum of (δ=3.87-4.40 ppm), H ｉ When calculated from the ratio of the integral values ​​of (δ = 9.76 ppm), the content of the group in which one hydrogen atom has been removed from dye 6 was 37 mass %, and the content of the group in which one hydrogen atom has been removed from secondary dye 4 relative to the total content of the groups in which one hydrogen atom has been removed from dye 6 and secondary dye 4 was 2.91 mol %.

[0796]

[0797] <Synthesis of EO Polymer 7'> EO Polymer 7', a polymer compound containing a group in which one hydrogen atom has been removed from Secondary Dye 4, was synthesized by the following steps.

[0798]

[0799] Methyl methacrylate (MMA) (1.73 g, 17.3 mmol) and a secondary dye-containing methacrylate monomer (0.5 g, 0.91 mmol) were dissolved in deoxygenated THF (2.5 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (18.1 mg) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then heated to 70°C and stirred for an additional 2 hours. After the reaction, the reaction solution was diluted with THF (23 mL), and the diluted solution was added dropwise to hexane (200 mL). The resulting solid was collected by filtration. The collected solid was rinsed with hexane (200 mL) and then vacuum dried. The dried solid was redissolved in THF (20 mL) and added dropwise to methanol (200 mL). The resulting solid was collected by filtration, rinsed with methanol (200 mL), and then vacuum dried to obtain EO polymer 7′ (1.72 g, yield 80%).

[0800] <Synthesis of EO Polymer 7> EO Polymer 7, a polymer compound containing a group in which one hydrogen atom has been removed from Dye 4, was synthesized by the following steps.

[0801]

[0802] In a 100 mL three-neck flask, under a nitrogen stream, ethanol (14 mL) was added to a THF (14 mL) solution of EO polymer 7' (0.7 g) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (375 mg), and the mixture was stirred at 50°C for 14 hours. After completion of the reaction, the reaction solution was added dropwise to hexane (280 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with hexane (140 mL) and then dried under vacuum. The resulting solid was redissolved in dichloromethane (20 mL), filtered, and the filtrate was added dropwise to methanol (100 mL). The resulting solid was collected by filtration, and the collected solid was rinsed with methanol (100 mL). The resulting solid was again redissolved in dichloromethane (20 mL), filtered, and the filtrate was added dropwise to methanol (100 mL). The resulting solid was collected by filtration, rinsed with methanol (100 mL), and vacuum-dried at 40° C. for 2 hours, and then vacuum-dried at 50° C. for 3 hours to obtain EO polymer 7 (609 mg).

[0803] The content of the group in which one hydrogen atom has been removed from dye 4 contained in EO polymer 7 was calculated from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom has been removed from dye 4 was 16% by mass.

[0804] <Synthesis of EO Polymer 8> EO Polymer 8, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 8, was synthesized by the following steps.

[0805]

[0806] Base polymer 1 (218 mg) and dye 8 (50 mg) were dissolved in anhydrous 1,4-dioxane (6.5 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (22 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (0.33 mL) and dibutyltin dilaurate (DBTDL) (22 μL) were added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 80°C to obtain EO polymer 8 (180 mg).

[0807] The content of the group obtained by removing one hydrogen atom from the dye 8 contained in the EO polymer 8 is expressed as １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ (δ=5.20 ppm) and H ｂ , H ｃ , H ｄ , and H ｅ The content was calculated from the ratio of the total integrated value of (δ=3.87-4.40 ppm) and was found to be 17% by mass.

[0808]

[0809] <Synthesis of EO Polymer 9> EO Polymer 9, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 8 and Sub Dye 8, was synthesized by the following steps.

[0810]

[0811] Base polymer 1 (218 mg), dye 8 (45 mg), and secondary dye 8 (5 mg) were dissolved in anhydrous 1,4-dioxane (6.5 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (22 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (0.33 mL) and dibutyltin dilaurate (DBTDL) (22 μL) were added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 80°C to obtain EO polymer 9 (180 mg).

[0812] The content of the group in which one hydrogen atom has been removed from dye 8 contained in EO polymer 9 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and it was found to be 16% by mass. １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ The integral value of and H ｂ The content was calculated from the ratio of the integral values ​​of the above and was found to be 23.10 mol %.

[0813]

[0814] <Synthesis of EO Polymer 10'> EO Polymer 10', a polymer compound containing a group in which one hydrogen atom has been removed from Secondary Dye 4, was synthesized by the following steps.

[0815]

[0816] Under a nitrogen stream, base polymer 3 (3.0 g) and secondary dye 4 (285 mg, 0.77 mmol) were dissolved in deoxygenated THF (62 mL), and 4-dimethylaminopyridine (DMAP) (5.68 mg, 46.3 mmol) was added, followed by stirring in an oil bath at 50°C for 2 hours. Subsequently, dehydrated methanol (1.9 mL) was added, and the mixture was stirred in an oil bath at 50°C for 4 hours. After air-cooling to room temperature, the reaction solution was added dropwise to methanol (200 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with methanol (150 mL) and dried in vacuo at 50°C to obtain EO polymer 10' (2.34 g).

[0817] The content of the group resulting from the removal of one hydrogen atom from secondary dye 4 contained in EO polymer 10' was determined from the ratio of mass extinction coefficients in absorbance measurement using a spectrophotometer, and the content of the group resulting from the removal of one hydrogen atom from secondary dye 4 was found to be 7.9% by mass. The glass transition temperature (Tg) was measured using a Shimadzu DSC-60APlus differential scanning calorimeter (DSC). The Tg was defined as the temperature corresponding to the intersection of the slope of the rising portion of the endothermic process of the baseline shift in the DSC curve showing the change in heat quantity when the temperature was increased at a rate of 10°C / min with the baseline. The glass transition temperature (Tg) of EO polymer 10' was measured using the same method as for EO polymer 1, and the Tg of EO polymer 10' was found to be 89°C.

[0818] The molecular weight of the obtained EO polymer 10′ was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel guard column Super AW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guard column Super AW-H, developing solvent: 0.5 mass % lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40° C.), and the weight average molecular weight Mw was 82,000 and the number average molecular weight Mn was 24,000.

[0819] <Synthesis of EO Polymer 10> EO Polymer 10, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 4, was synthesized by the following steps.

[0820]

[0821] Under a nitrogen stream, EO polymer 10' (2.2 g) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (711 mg, 2.3 mmol) were dissolved in deoxygenated THF (40 mL), and then dehydrated ethanol (40 mL) was added. The mixture was heated to 50°C and stirred for 8 hours. After air-cooling to room temperature, the reaction solution was added dropwise to methanol (440 mL). The resulting solid was collected by filtration and rinsed with methanol (220 mL) to obtain a green solid. The green solid was redissolved in dichloromethane (80 mL) and filtered, and the filtrate was concentrated using an evaporator. The concentrate was redissolved in dichloromethane (80 mL) and added dropwise to hexane (800 mL). The resulting filtered product was rinsed with hexane (200 mL) and vacuum dried to obtain EO polymer 10 (1.96 g).

[0822] The content of the group in EO polymer 10 in which one hydrogen atom has been removed from dye 4 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom has been removed from dye 4 was 13% by mass. The glass transition temperature (Tg) of EO polymer 10 was measured using the same method as for EO polymer 1, and the Tg of EO polymer 10 was found to be 105°C. Since the peak of the aldehyde group in the raw material EO polymer 10' was below the detection limit, it was confirmed that the content of the group in EO polymer 10 in which one hydrogen atom has been removed from secondary dye 4 was less than 0.01 mol%.

[0823] The molecular weight of the obtained base polymer 10 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel guard column Super AW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guard column Super AW-H, developing solvent: 0.5 mass % lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight average molecular weight Mw was 460,000 and the number average molecular weight Mn was 150,000.

[0824] <Synthesis of EO Polymer 11'> EO polymer 11', which is a polymer compound containing a group in which one hydrogen atom has been removed from secondary dye 4, was synthesized by the following steps.

[0825]

[0826] Under a nitrogen stream, base polymer 4 (1.02 g) and secondary dye 4 (285 mg, 0.72 mmol) were dissolved in anhydrous chloroform (30.4 mL). 4-dimethylaminopyridine (DMAP) (884 mg, 7.2 mmol) was added, and the mixture was stirred in an oil bath at 60°C for 6 hours. Subsequently, anhydrous methanol (0.56 mL) was added, and the mixture was stirred in an oil bath at 60°C for 3 hours. After air-cooling to room temperature, the reaction solution was added dropwise to methanol (300 mL), and the resulting solid was collected by filtration. The collected solid was rinsed with methanol (100 mL) and dried under vacuum at 60°C to obtain EO polymer 11'. The content of the group resulting from the removal of one hydrogen atom from secondary dye 4 in EO polymer 11' was determined from the ratio of mass extinction coefficients in absorbance measurement using a spectrophotometer. The content of the group resulting from the removal of one hydrogen atom from secondary dye 4 was found to be 7.6% by mass.

[0827] <Synthesis of EO Polymer 11> EO Polymer 11, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 4, was synthesized by the following steps.

[0828]

[0829] Under a nitrogen stream, EO polymer 11' (0.5 g) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (283 mg, 0.9 mmol) were dissolved in deoxygenated THF (50 mL), and then dehydrated ethanol (25 mL) was added and the mixture was stirred for 12 hours under heating at 60°C. After air-cooling to room temperature, the reaction solution was concentrated using an evaporator. The concentrate was redissolved in dichloromethane (10 mL) and added dropwise to methanol (100 mL). The resulting solid was collected by filtration and rinsed with methanol (100 mL) to obtain a green solid.

[0830] Under a nitrogen stream, the resulting green solid (0.1 g) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (57 mg, 0.18 mmol) were dissolved in deoxygenated THF (10 mL), and then dehydrated ethanol (5 mL) was added and the mixture was stirred at 60°C for 6 hours. After air-cooling to room temperature, the reaction solution was concentrated using an evaporator. The concentrate was redissolved in dichloromethane (10 mL) and added dropwise to methanol (100 mL). The resulting solid was collected by filtration and rinsed with methanol (100 mL). After washing, the solid was redissolved in dichloromethane (10 mL), activated clay (100 mg) was added, and the mixture was stirred at room temperature for 30 minutes, after which the clay was removed by filtration. Activated clay (100 mg) was added to the filtrate, and the mixture was further stirred at room temperature for 30 minutes, after which the activated clay was removed by filtration. The obtained filtrate was concentrated using an evaporator, then redissolved in dichloromethane (10 mL) and added dropwise to methanol (100 mL). The resulting solid was collected by filtration and rinsed with methanol (100 mL). After washing, the solid was redissolved in dichloromethane (10 mL) and added dropwise to hexane (100 mL). The resulting solid was collected by filtration, rinsed with hexane (100 mL), and then vacuum-dried at 60°C for 6 hours to obtain EO polymer 11 (80 mg).

[0831] The content of the group in EO polymer 11 in which one hydrogen atom has been removed from dye 4 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and was found to be 9.1 mass %. Since the peak of the aldehyde group in the raw material EO polymer 11' was below the detection limit, it was confirmed that the content of the group in EO polymer 11 in which one hydrogen atom has been removed from secondary dye 4 was less than 0.01 mol %.

[0832] <Synthesis of EO Polymer 12> EO Polymer 12, which is a polymer compound containing groups in which one hydrogen atom has been removed from each of Dye 4 and Sub Dye 4, was synthesized by the following steps.

[0833]

[0834] Under a nitrogen stream, EO polymer 11' (0.5 g) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (283 mg, 0.9 mmol) were dissolved in deoxygenated THF (50 mL), and then dehydrated ethanol (25 mL) was added. The mixture was heated to 60°C and stirred for 12 hours. After air-cooling to room temperature, the reaction solution was concentrated using an evaporator. The concentrate was redissolved in dichloromethane (10 mL) and added dropwise to methanol (100 mL). The resulting solid was collected by filtration and rinsed with methanol (100 mL) to obtain a green solid. After washing, the green solid was redissolved in dichloromethane (10 mL), activated clay (500 mg) was added, and the mixture was stirred at room temperature for 30 minutes. The clay was then removed by filtration. Activated clay (500 mg) was added to the filtrate, and the mixture was stirred at room temperature for another 30 minutes. The activated clay was then removed by filtration. The resulting filtrate was concentrated using an evaporator, redissolved in dichloromethane (20 mL), and added dropwise to methanol (200 mL). The resulting solid was collected by filtration and rinsed with methanol (100 mL). After washing, the solid was redissolved in dichloromethane (20 mL) and added dropwise to hexane (200 mL). The resulting solid was collected by filtration, rinsed with hexane (100 mL), and then vacuum-dried at 60°C for 6 hours to obtain EO polymer 12 (480 mg).

[0835] The content of the group in which one hydrogen atom has been removed from dye 4 contained in EO polymer 12 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and was found to be 9.5% by mass. １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ The integral value of and H ｂ The integral value of H ｃ The content was calculated from the ratio of the integral values ​​of

[0836] The molecular weight of the obtained EO polymer 12 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel guard column Super AW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guard column Super AW-H, developing solvent: 0.5 mass % lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight average molecular weight Mw was 85,000 and the number average molecular weight Mn was 32,000.

[0837]

[0838] <Synthesis of EO Polymer 13'> EO Polymer 13', a polymer compound containing a group in which one hydrogen atom has been removed from Secondary Dye 4, was synthesized by the following steps.

[0839]

[0840] Under a nitrogen stream, base polymer 5 (1.5 g) and secondary dye 4 (398 mg, 1.01 mmol) were dissolved in anhydrous chloroform (50.6 mL), and 4-dimethylaminopyridine (DMAP) (1.24 g, 10.0 mmol) was added. The mixture was then stirred in an oil bath at 60°C for 6 hours. Subsequently, anhydrous methanol (2.0 mL) was added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After air-cooling to room temperature, the reaction solution was concentrated using an evaporator, redissolved in dichloromethane (10 mL), and added dropwise to methanol (500 mL). The resulting solid was collected by filtration and rinsed with methanol (200 mL). The collected material was dissolved in dichloromethane (10 mL) and added dropwise to methanol (200 mL). The resulting solid was collected by filtration and rinsed with methanol (50 mL). The product was redissolved in dichloromethane (10 mL) and added dropwise to hexane (200 mL). The resulting solid was collected by filtration, rinsed with hexane (100 mL), and then vacuum dried to obtain EO polymer 13′ (854 mg).

[0841] The glass transition temperature (Tg) of EO Polymer 13' was measured in the same manner as for EO Polymer 1, and the Tg of EO Polymer 13' was found to be 123°C.

[0842] The content of the group in which one hydrogen atom has been removed from secondary dye 4 contained in EO polymer 13' was determined from the ratio of mass extinction coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom has been removed from secondary dye 4 was 26% by mass. The molecular weight of the obtained EO polymer 10' was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel guard column Super AW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guard column Super AW-H, developing solvent: 0.5% by mass lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight average molecular weight Mw was 210,000 and the number average molecular weight Mn was 56,000.

[0843] <Synthesis of EO Polymer 13> EO Polymer 13, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 4, was synthesized by the following steps.

[0844]

[0845] Under a nitrogen stream, EO polymer 13' (767 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (595 mg, 1.9 mmol) were dissolved in deoxygenated THF (15 mL), and then dehydrated ethanol (15 mL) was added. The mixture was stirred at 50°C for 15 hours. After air-cooling to room temperature, the reaction solution was concentrated using an evaporator. The concentrate was redissolved in dichloromethane (12 mL) and added dropwise to methanol (120 mL). The resulting solid was collected by filtration and rinsed with methanol (120 mL) to obtain a green solid. After washing, the solid was redissolved in dichloromethane (12 mL), activated clay (120 mg) was added, and the mixture was stirred at room temperature for 30 minutes. The clay was then removed by filtration. Activated clay (120 mg) was added to the filtrate, and the mixture was stirred at room temperature for an additional 30 minutes. The activated clay was then removed by filtration. The resulting filtrate was concentrated using an evaporator, redissolved in dichloromethane (12 mL), and added dropwise to methanol (120 mL). The resulting solid was collected by filtration and rinsed with methanol (120 mL). After washing, the solid was vacuum-dried at 50°C for 4 hours to obtain EO polymer 13 (756 mg). The glass transition temperature (Tg) of EO polymer 13 was measured using the same method as for EO polymer 1, and the Tg of EO polymer 13 was found to be 150°C.

[0846] The content of the group in EO polymer 13 in which one hydrogen atom has been removed from dye 4 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and was found to be 35 mass%. Since the peak of the aldehyde group in the raw material EO polymer 13' was below the detection limit, it was confirmed that the content of the group in EO polymer 13 in which one hydrogen atom has been removed from secondary dye 4 was less than 0.01 mol%.

[0847] The molecular weight of the obtained EO polymer 13 was determined by GPC using a GPC system (liquid delivery system: LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel guard column Super AW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guard column Super AW-H, developing solvent: 0.5 mass % lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight average molecular weight Mw was 240,000 and the number average molecular weight Mn was 83,000.

[0848] <Synthesis of EO Polymer 14'> EO polymer 14', a polymer compound containing a group in which one hydrogen atom has been removed from secondary dye 9, was synthesized by the following steps.

[0849]

[0850] Under a nitrogen stream, base polymer 6 (2.00 g, 18.4 mmol) and compound 18 (654 mg, 0.92 mmol) were dissolved in anhydrous DMF (36.7 mL), and potassium carbonate (7.61 g, 55.2 mmol) was added. The mixture was then stirred at room temperature for 50 minutes. The temperature was then raised to 50°C and the mixture was stirred for 3.5 hours. 1-Iodohexane (1.4 mL) was added to the reaction solution, and the mixture was further stirred at 50°C for 3.5 hours. After air-cooling to room temperature, the reaction solution was filtered, concentrated, and dispersed in methanol (100 mL). The methanol dispersion was sonicated, and the solid was collected by filtration. The collected material was then washed with methanol (100 mL), isopropyl alcohol (100 mL), and hexane (100 mL). The resulting solid was dried in vacuum at 50°C for 4 hours to obtain EO polymer 14' (2.31 g, yield 79.9%).

[0851] The content of the group in which one hydrogen atom has been removed from secondary dye 9 contained in EO polymer 14′ was calculated from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom has been removed from secondary dye 9 was 17% by mass.

[0852] <Synthesis of EO Polymer 14> EO Polymer 14, a polymer compound containing a group in which one hydrogen atom has been removed from Dye 9, was synthesized by the following steps.

[0853]

[0854] Under a nitrogen stream, EO polymer 14' (1.31 g, 8.44 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (303 mg, 0.96 mmol) were dissolved in deoxygenated THF (26.2 mL), followed by the addition of dehydrated ethanol (26.2 mL) and stirring at 50°C for 15 hours. After cooling to room temperature, the reaction solution was poured into a mixture of methanol and ultrapure water (mixing ratio 1:1, 520 mL) and stirred at room temperature for 30 minutes. The resulting solid was collected by filtration and washed with methanol (260 mL). The collected product was redissolved in dichloromethane (42 mL) and filtered. Activated clay (1.4 g) was added to the filtrate and stirred at room temperature for 30 minutes. After removing the clay by filtration, activated clay (1.4 g) was added to the filtrate again and stirred at room temperature for another 30 minutes. The activated clay was then removed by filtration, and the resulting filtrate was concentrated using an evaporator. The resulting solid was redissolved in dichloromethane (15 mL) and added dropwise to methanol (700 mL). The resulting solid was filtered, rinsed with methanol (250 mL), and vacuum dried to obtain EO polymer 14 (1.17 g, yield 83.0%). The glass transition temperature (Tg) of EO polymer 14 was measured using the same method as for EO polymer 1, and the Tg of EO polymer 14 was found to be 80°C.

[0855] The content of the group in EO polymer 14 in which one hydrogen atom has been removed from dye 9 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and was found to be 24% by mass. Since the peak of the aldehyde group in the raw material EO polymer 14' was below the detection limit, it was confirmed that the content of the group in EO polymer 14 in which one hydrogen atom has been removed from secondary dye 9 was less than 0.01 mol%.

[0856] <Synthesis of EO Polymer 15> EO Polymer 15, a polymer compound containing groups in which one hydrogen atom has been removed from each of Dye 9 and Sub Dye 9, was synthesized by the following steps.

[0857]

[0858] Under a nitrogen stream, EO polymer 14' (0.50 g, 3.14 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (35.7 mg, 2.98 mmol) were dissolved in deoxygenated THF (10 mL), and then dehydrated ethanol (10 mL) was added and the mixture was stirred at 50°C for 15 hours. 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (10.2 mg, 0.85 mmol) was added, and the mixture was stirred at 50°C for an additional 6 hours. After cooling to room temperature, the reaction solution was poured into a mixture of methanol and ultrapure water (mixing ratio 1:1, 200 mL) and stirred at room temperature for 20 minutes. The resulting solid was collected by filtration and washed with methanol (100 mL). The filtered product was redissolved in dichloromethane (15.3 mL) and filtered. Activated clay (510 mg) was added to the filtrate, and the mixture was stirred at room temperature for 30 minutes. After removing the clay by filtration, activated clay (510 mg) was again added to the filtrate, and the mixture was stirred at room temperature for another 30 minutes. The activated clay was then removed by filtration, and the resulting filtrate was concentrated using an evaporator. The residue was redissolved in dichloromethane (15 mL) and added dropwise to methanol (250 mL). The resulting solid was collected by filtration, rinsed with methanol (250 mL), and vacuum-dried to obtain EO polymer 15 (409 mg, yield 78.2%). The glass transition temperature (Tg) of EO polymer 15 was measured using the same method as for EO polymer 1, and the Tg of EO polymer 15 was found to be 70°C.

[0859] The content of the group in which one hydrogen atom has been removed from dye 9 contained in EO polymer 15 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom has been removed from dye 9 was 17% by mass. １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ The integral value of and H ｂ The integral value of H ｃThe content was calculated from the ratio of the integral values ​​of

[0860]

[0861] <Synthesis of EO Polymer 16> EO Polymer 16, which is a polymer compound containing a group in which one hydrogen atom has been removed from Dye 4, was synthesized by the following steps.

[0862]

[0863] Base polymer 1 (1.42 g) and dye 4 (500 mg) were dissolved in anhydrous 1,4-dioxane (44 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (146 μL) was added. The mixture was stirred for 3 hours in an oil bath at 110 °C. Subsequently, anhydrous methanol (1.56 mL) and dibutyltin dilaurate (DBTDL) (146 μL) were added, and the mixture was stirred for 2 hours in an oil bath at 110 °C. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (300 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 60 °C to obtain EO polymer 16 (1.45 g). The content of the group in EO polymer 16 in which one hydrogen atom had been removed from dye 4 was determined from the ratio of mass extinction coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom had been removed from dye 4 was 28% by mass. The glass transition temperature (Tg) of EO polymer 16 was measured using the same method as for EO polymer 1, and the Tg of EO polymer 16 was found to be 151°C. The peaks of the aldehyde groups in the raw material precursor of dye 4 (secondary dye 1) and secondary dye 4 in which the tert-butyldimethylsilyl group of secondary dye 1 was substituted with hydrogen were below the detection limit, confirming that the contents of secondary dyes 1 and 4 in EO polymer 16 were less than 0.01 mol%.

[0864] <Synthesis of EO Polymer 17> EO Polymer 17, a polymer compound containing groups in which one hydrogen atom has been removed from each of Dye 4 and Sub Dye 4, was synthesized by the following steps.

[0865]

[0866] Base polymer 1 (412 mg), dye 4 (182 mg), and secondary dye 4 (18 mg) were dissolved in anhydrous 1,4-dioxane (13.2 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (44 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (13.2 mL) and dibutyltin dilaurate (DBTDL) (44 μL) were added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 60°C to obtain EO polymer 17 (0.48 g). The glass transition temperature (Tg) of EO Polymer 17 was measured in the same manner as for EO Polymer 1, and the Tg of EO Polymer 17 was found to be 150°C.

[0867] The content of the group in which one hydrogen atom has been removed from dye 4 contained in EO polymer 17 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and was found to be 26% by mass. １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ The integral value of and H ｂ The integral value of H ｃ The content was calculated from the ratio of the integral values ​​of the above and was found to be 15.00 mol %.

[0868]

[0869] <Synthesis of EO Polymer 18> EO Polymer 18, a polymer compound containing groups in which one hydrogen atom has been removed from each of Dye 4 and Sub Dye 4, was synthesized by the following steps.

[0870]

[0871] Base polymer 1 (412 mg), dye 4 (161 mg), and secondary dye 4 (39 mg) were dissolved in anhydrous 1,4-dioxane (13.2 mL) under a nitrogen stream, and dibutyltin dilaurate (DBTDL) (44 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, anhydrous methanol (13.2 mL) and dibutyltin dilaurate (DBTDL) (44 μL) were added, and the mixture was stirred in an oil bath at 110°C for 2 hours. After air-cooling to room temperature, the reaction solution was added dropwise to hexane (200 mL), and the resulting solid was collected by filtration. The collected solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (good solvent: DCM, poor solvent: methanol), and then vacuum-dried at 60°C to obtain EO polymer 18 (0.48 g). The glass transition temperature (Tg) of EO Polymer 18 was measured in the same manner as for EO Polymer 1, and the Tg of EO Polymer 18 was found to be 150°C.

[0872] The content of the group in which one hydrogen atom has been removed from dye 4 contained in EO polymer 18 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and was found to be 23 mass %. １ H-NMR (heavy solvent: CDCl ３ ) H of the following formula measured ａ The integral value of and H ｂ The integral value of H ｃ The content was calculated from the ratio of the integral values ​​of the above and was found to be 30.00 mol %.

[0873]

[0874] <Synthesis of EO Polymer 19'> EO Polymer 19', a polymer compound containing a group in which one hydrogen atom has been removed from Secondary Dye 4, was synthesized by the following steps.

[0875]

[0876] Under a nitrogen stream, base polymer 5 (1.45 g) and secondary dye 4 (236 mg, 0.60 mmol) were dissolved in anhydrous chloroform (50 mL), and 4-dimethylaminopyridine (DMAP) (733 mg, 6.0 mmol) was added. The mixture was then stirred in an oil bath at 60°C for 6 hours. Subsequently, anhydrous methanol (1.2 mL) was added, and the mixture was stirred in an oil bath at 60°C for 4 hours. After air-cooling to room temperature, the reaction solution was concentrated using an evaporator, redissolved in dichloromethane (30 mL), and added dropwise to methanol (200 mL). The resulting solid was collected by filtration and rinsed with methanol (100 mL). The collected product was dissolved in dichloromethane (10 mL) and added dropwise to methanol (300 mL). The resulting solid was collected by filtration and rinsed with methanol (100 mL). The product was redissolved in dichloromethane (10 mL) and added dropwise to hexane (200 mL). The resulting solid was collected by filtration, rinsed with hexane (100 mL), and then vacuum dried to obtain EO polymer 19′ (587 mg).

[0877] The content of the group in which one hydrogen atom has been removed from secondary dye 4 contained in EO polymer 19′ was calculated from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and the content of the group in which one hydrogen atom has been removed from secondary dye 4 was 16 mass%.

[0878] <Synthesis of EO Polymer 19> EO Polymer 19, a polymer compound containing a group in which one hydrogen atom has been removed from Dye 4, was synthesized by the following steps.

[0879]

[0880] Under a nitrogen stream, EO polymer 19' (530 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (267 mg, 0.85 mmol) were dissolved in deoxygenated THF (10.6 mL), and then dehydrated ethanol (10.6 mL) was added. The mixture was heated to 50°C and stirred for 15 hours. After air-cooling to room temperature, the reaction solution was concentrated using an evaporator. The concentrate was redissolved in dichloromethane (10 mL) and added dropwise to methanol (100 mL). The resulting solid was collected by filtration and rinsed with methanol (100 mL) to obtain a green solid. After washing, the solid was redissolved in dichloromethane (7 mL), activated clay (700 mg) was added, and the mixture was stirred at room temperature for 30 minutes. The clay was then removed by filtration. Activated clay (700 mg) was added to the filtrate, and the mixture was stirred at room temperature for an additional 30 minutes. The activated clay was then removed by filtration. The resulting filtrate was concentrated using an evaporator, redissolved in dichloromethane (10 mL), and added dropwise to methanol (70 mL). The resulting solid was collected by filtration and rinsed with methanol (70 mL). After washing, the solid was vacuum-dried at 50°C for 4 hours to obtain EO polymer 19 (432 mg). The glass transition temperature (Tg) of EO polymer 19 was measured using the same method as for EO polymer 1, and the Tg of EO polymer 19 was found to be 151°C.

[0881] The content of the group in EO polymer 19 in which one hydrogen atom has been removed from dye 4 was determined from the ratio of mass absorption coefficients in absorbance measurement using a spectrophotometer, and was found to be 26% by mass. Since the peak of the aldehyde group in the raw material EO polymer 19' was below the detection limit, it was confirmed that the content of the group in EO polymer 19 in which one hydrogen atom has been removed from secondary dye 4 was less than 0.01 mol%.

[0882] <Synthesis of EO Polymer 20> EO polymer 20, which is a polymer compound containing a group in which one hydrogen atom has been removed from dye 4 and sub-dye 4, was synthesized by the following steps.

[0883]

[0884] Under a nitrogen stream, EO polymer 13' (235 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (41.8 mg, 0.13 mmol) were dissolved in deoxygenated THF (12 mL), and then dehydrated ethanol (6.0 mL) was added. The mixture was stirred at 60°C for 8 hours. After air-cooling to room temperature, the reaction solution was concentrated using an evaporator. The concentrate was redissolved in dichloromethane (10 mL) and added dropwise to methanol (100 mL). The resulting solid was collected by filtration and rinsed with methanol (50 mL) to obtain a green solid. After washing, the solid was redissolved in dichloromethane (10 mL), activated clay (235 mg) was added, and the mixture was stirred at room temperature for 30 minutes. The clay was then removed by filtration. Activated clay (250 mg) was added to the filtrate, and the mixture was stirred at room temperature for an additional 30 minutes. The activated clay was then removed by filtration. The resulting filtrate was concentrated using an evaporator, redissolved in dichloromethane (10 mL), and added dropwise to methanol (100 mL). The...

Claims

1. A composition comprising a compound represented by the following formula (1) and a compound represented by the following formula (3), wherein the content of the compound represented by the following formula (3) is 0.0001 mol % or more and 25 mol % or less based on the total content of the compound represented by the following formula (1) and the compound represented by the following formula (3). [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15. [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent. [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

2. In the formula (3), Z ３１ is a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a cyano group, an aldehyde group, or a carboxy group.

3. Y in the formula (1) １１ are each independently represented by the following formula (4), and Y in the formula (3) ３１ are each independently represented by the following formula (5), provided that n １１ When R is 2 or more, R in the following formula (4) ４１ and R ４２ is another Y １１ R included in ４１ or R ４２ may be linked to form a ring, and n in the formula (3) ３１ When R is 2 or more, R in the following formula (5) ５１ and R ５２ is another Y ３１ R included in ５１ or R ５２ The composition according to claim 1 , wherein the compound is optionally linked to form a ring. [In formula (4), R ４１ and R ４２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ４１ and R ４２ may be bonded to form a ring. [In formula (5), R ５１ and R ５２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ５１ and R ５２ may be bonded to form a ring.

4. Y in the formula (1) １１ and Y in the formula (3) ３１ are each independently represented by the following formula (6), the following formula (7), or the following formula (8), provided that n １１ When R is 2 or more, R in the following formula (6), the following formula (7), or the following formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y １１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ may be linked to form a ring, and n in the formula (3) ３１ When R is 2 or more, R in the following formula (6), the following formula (7), or the following formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y ３１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ The composition according to claim 1 , wherein the compound is optionally linked to form a ring. [In formula (6), R ６１ and R ６２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ６１ and R ６２ may be bonded to form a ring. [In formula (7), R ７１ and R ７２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ７１ and R ７２ may be bonded to form a ring, ７１ is O, S or N-Q ７１ and Q ７１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent. [In formula (8), R ８１ ~R ８７ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ８１ ~R ８７ At least two of these may be bonded to form a ring.

5. n in the formula (1) １１ is n in the formula (3). ３１ The composition of claim 1 , wherein the 6. Z in the formula (1) １１ and Z in the formula (3) ３１ and R in the formula (1) １４ and R in the formula (3) ３４ The composition according to claim 1 , wherein the structure of the compound represented by formula (1) and the structure of the compound represented by formula (3) are identical, except for:

7. The composition of claim 1, comprising a polymeric material.

8. The composition according to claim 7, wherein the polymer material is at least one selected from the group consisting of polymethyl(meth)acrylate, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, and copolymers thereof.

9. The composition of claim 1, comprising an organic solvent.

10. A composition comprising a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1), and a compound represented by the following formula (3): [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15. [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent. [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

11. A composition comprising a compound represented by the following formula (1) and a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3): [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15. [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent. [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

12. A composition comprising a nonlinear optically active polymer compound having, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1), and a nonlinear optically active polymer compound having, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3): [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15. [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent. [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

13. A composition comprising a nonlinear optically active polymer compound containing, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1) and a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3), wherein the content of the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3) in the nonlinear optically active polymer compound is 0.0001 mol % or more and 25 mol % or less of the total content of the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1) and the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3). [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15. [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent. [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

14. A nonlinear optical element comprising a film formed from the composition according to any one of claims 1 to 13.

15. The nonlinear optical element according to claim 14, which operates based on the electro-optic effect.

16. An optical modulator comprising the nonlinear optical element according to claim 14.

17. A polymer compound comprising, as at least one selected from a substituent and a main chain, a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1) and a group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3), wherein the content of the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3) is 0.0001 mol % or more and 25 mol % or less of the total content of the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (1) and the group obtained by removing at least one hydrogen atom from a compound represented by the following formula (3). [In formula (1), Ar １１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, １１ and R １３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R １２ and R １４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; １１ each independently represents a divalent π-conjugated linking group which may have a substituent, １１ is a group represented by formula (2), and m １１ are each independently an integer of 0 to 5, １２ is an integer from 1 to 5, and m １３ is an integer from 0 to 5, １１ is an integer from 1 to 15. [In formula (2), *J ２１ Is Y １１ is the bonding position with R ２１ and R ２２ each independently represents a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ２１ and R ２２ may be bonded to form a ring, or R ２１ and R ２２ is R ２１ and R ２２ and may form a carbonyl group together with the carbon atom to which they are attached, R ２３ and R ２４ each independently represents a cyano group, an alkyloxycarbonyl group having 1 to 10 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 10 carbon atoms which may have a substituent, ２１ is O, S or N-Q ２１ and Q ２１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group having 1 to 10 carbon atoms which may have a substituent. [In formula (3), Ar ３１ are each independently a divalent group selected from an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, and an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ and R ３３ are each independently a divalent group selected from a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent; R ３２ and R ３４ each independently represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, a hydroxy group or a halogen atom; ３１ each independently represents a divalent π-conjugated linking group which may have a substituent, ３１ represents a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, an amino group which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a boryl group which may have a substituent, a halogen atom, a cyano group, an aldehyde group, a hydroxy group, or a carboxy group. ３１ does not include the group represented by formula (2). ３５ and R ３６ each independently represents an alkyl group having 1 to 50 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, ３１ are each independently an integer of 0 to 5, ３２ is an integer from 1 to 5, and m ３３ is an integer from 0 to 5, ３１ is an integer from 0 to 15. ３１ If is 0, Z ３１ is not a hydrogen atom.

18. The group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is at least R １４ and the group obtained by removing at least one hydrogen atom from the compound represented by formula (3) is at least R ３４ The polymer compound according to claim 17, wherein a hydrogen atom is removed from 19. In the formula (3), Z ３１ is a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, -C(O)-R ３５ , -C(O)O-R ３５ , -C(O)NH-R ３５ , -C(O)N(R ３５ ) (R ３６ ), a cyano group, an aldehyde group, or a carboxy group.

20. Y in the formula (1) １１ are each independently represented by the following formula (4), and Y in the formula (3) ３１ are each independently represented by the following formula (5), provided that n １１ When R is 2 or more, R in the following formula (4) ４１ and R ４２ is another Y １１ R included in ４１ or R ４２ may be linked to form a ring, and n in the formula (3) ３１ When R is 2 or more, R in the following formula (5) ５１ and R ５２ is another Y ３１ R included in ５１ or R ５２ The polymer compound according to claim 17 , which may be linked to form a ring. [In formula (4), R ４１ and R ４２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ４１ and R ４２ may be bonded to form a ring. [In formula (5), R ５１ and R ５２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ５１ and R ５２ may be bonded to form a ring.

21. Y in the formula (1) １１ and Y in the formula (3) ３１ are each independently represented by the following formula (6), the following formula (7), or the following formula (8), provided that n １１ When R is 2 or more, R in the following formula (6), the following formula (7), or the following formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y １１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ may be linked to form a ring, and n in the formula (3) ３１ When R is 2 or more, R in the following formula (6), the following formula (7), or the following formula (8) ６１ and R ６２ , R ７１ and R ７２ , or R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ and R ８７ is another Y ３１ R included in ６１ , R ６２ , R ７１ , R ７２ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , R ８６ or R ８７ The polymer compound according to claim 17 , which may be linked to form a ring. [In formula (6), R ６１ and R ６２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ６１ and R ６２ may be bonded to form a ring. [In formula (7), R ７１ and R ７２ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ７１ and R ７２ may be bonded to form a ring, ７１ is O, S or N-Q ７１ and Q ７１ is a branched, linear or cyclic saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms, and / or silicon atoms, or an aralkyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent. [In formula (8), R ８１ ~R ８７ are each independently a hydrogen atom, a branched, linear or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, some of the carbon atoms of which may be substituted with oxygen atoms, sulfur atoms and / or silicon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom or a boryl group which may have a substituent; ８１ ~R ８７ At least two of these may be bonded to form a ring.

22. n in the formula (1) １１ is n in the formula (3). ３１ The polymer compound according to claim 17, wherein 23. A nonlinear optical element comprising a film formed from the polymer compound according to any one of claims 17 to 22.

24. The nonlinear optical element according to claim 23, which operates based on the electro-optic effect.

25. An optical modulator comprising the nonlinear optical element according to claim 23.

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