Polymer compound, composition, nonlinear optical element, and optical modulator

Abstract

The objective of the present invention is to: provide a polymer compound having improved filterability and excellent thermal stability by suppressing viscosity increase and gelation during heating; provide a composition that includes the polymer compound; provide a nonlinear optical element that uses the composition; and provide an optical modulator that comprises the nonlinear optical element and that operates on the basis of an electro-optic effect. The present invention relates to a polymer compound including at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1-1), a repeating unit represented by formula (1-2), and a repeating unit represented by formula (1-3), in the description.

Description

Polymer compounds, compositions, nonlinear optical elements, and optical modulators

[0001] The present invention relates to polymer compounds, compositions, nonlinear optical elements, and optical modulators.

[0002] In recent years, the development of various optoelectronic devices using nonlinear optical materials has been progressing in fields such as optical information processing and optical communication. Nonlinear optical materials refer to materials that exhibit a polarization response proportional to the square, cube, or higher-order terms of the magnitude of the electric field of light. Among these, nonlinear optical materials 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 mixing or bonding compounds (dyes) having nonlinear optical activity to polymer materials such as polymethyl methacrylate (PMMA). Nonlinear optical properties are expressed by the electro-optic coefficient (hereinafter also referred to as the "EO coefficient" in this specification), and are also denoted as r33. As dyes, so-called push-pull type π-conjugated compounds are known, which have electron-donating groups and electron-withdrawing groups located at both ends of the molecular structure, and a π-conjugated chain connecting them.

[0004] The electro-optic effect is induced by orienting a nonlinear optical material to a state lacking inversion symmetry. Therefore, when using organic nonlinear optical materials in nonlinear optical elements, it is necessary to keep the dye in a specific orientation. To create this orientation, it is necessary to perform an operation (poling treatment) on the organic nonlinear optical material by applying a high voltage at a temperature near the glass transition temperature of the polymer material (Patent Documents 1-4).

[0005] For example, Patent Document 5 discloses a nonlinear optically active copolymer in which the relaxation of the orientation state of the dye due to heat is suppressed by introducing a dye having nonlinear optical activity via an isocyanate group into a polymer material having a high glass transition temperature.

[0006] However, when isocyanate groups are used as bonding groups between polymer materials and dyes having nonlinear optical activity, for example, in the process of heat-drying (solvent removal) a polymer material into which a dye having nonlinear optical activity has been introduced via isocyanate groups, the isocyanate groups generated by the detachment of the dye from the polymer material react with moisture in the solvent or other isocyanate groups to form a network structure, increasing viscosity due to the increase in molecular weight and leading to gelation, thus causing problems with thermal stability. Furthermore, the dye introduced via isocyanate groups is transmitted via urethane bonds, and the deterioration of these urethane bonds over time due to moisture in the atmosphere and heat also contributes to reduced thermal stability. Non-patent document 1 also describes a method for forming a uniform film by mixing a polymer compound (diene) in which anthracene is substituted with a maleimide polymer and a low-molecular-weight compound (dienophile) in which a maleimide substituent is introduced into a dye having nonlinear optical activity, coating the mixture, and then heating it to perform a Diels-Alder reaction. However, when a low-molecular-weight compound in which a maleimide substituent has been introduced into a dye with nonlinear optical activity is heated, a side reaction occurs in which the maleimide substituent corresponding to the dienophile reacts with the polymer compound substituted with anthracene, causing the dye with nonlinear optical activity to react as a diene, resulting in a decrease in nonlinear optical activity.

[0007] International Publication No. 2019 / 151318, Japanese Patent Publication No. 2010-066325, International Publication No. 2011 / 024774, Japanese Patent Publication No. 2015-178544, International Publication No. 2017 / 159815

[0008] Chem. Mater. 2010, Vol. 22, pp. 5601-5608

[0009] The object of the present invention is to provide a polymer compound with improved filterability and excellent thermal stability by suppressing viscosity increase and gelation during heating, and in addition, to provide a composition containing the polymer compound. Another object of the present invention is to provide a nonlinear optical element using the above composition, and to provide an optical modulator equipped with the nonlinear optical element that operates based on the electro-optic effect.

[0010] As a result of intensive studies in view of the above problems, the inventors of the present invention have found that by making the binding site between a polymer material and a compound (dye) having non-linear optical activity have a specific structure, an increase in viscosity and gelation during heating are suppressed, and further, by having a highly heat-resistant linking group, high thermal stability is exhibited, and thus the present invention has been completed.

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

[0012] Aspect 1 of the present invention relates to a polymer compound containing at least one selected from the group consisting of a repeating unit represented by the following formula (1-1), a repeating unit represented by the following formula (1-2), and a repeating unit represented by the following formula (1-3).

[0013]

[0014] [In formula (1-1), R １１１ to R １１３ are each independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, or a halogen atom, and L １１１ and L １１２ each independently represent a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group group A which may have a substituent, X １１１ is a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), Y １１１ and Y １１２ are each independently an oxygen atom or N-Z １１１ and Z １１１ is a hydrogen atom, a group selected from the following hydrocarbon group group A which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, and n １１１ represents 0 to 1. ]

[0015]

[0016] [In formula (1-2), R １２１ and R １２２ each independently represent a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, or a halogen atom, and L １２１Each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A, which may have substituents, or a divalent aromatic group which may have substituents, X １２１ n is a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), and n １２１ [This is an integer between 1 and 5.]

[0017]

[0018] [In formula (1-3), R １３１ ~R １３３ Each independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom, R １３４ Each of these is independently a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, n １３２ If the number is 2 or more, the R １３４ is another R １３４ It may also be bonded to form a ring, R １３５ Each is independently a single bond, an optionally substituted divalent alkyl group, an optionally substituted divalent aromatic group, or an optionally substituted divalent aralkyl group, X １３１ Each of these is independently a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), n １３１ n is an integer between 1 and 5. １３２ n is an integer between 0 and 4, where n １３１ to n １３２ The sum of the numbers is 5 or less.

[0019]

[0020] [In formula (2), Ar ２１ Each of these is independently a divalent aromatic group which may have substituents, and R ２１ and R ２３ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A, which may have substituents, or a divalent aromatic group which may have substituents, and R ２２ and R ２４Each independently represents a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ２１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ２１ This is a group represented by the following formula (3), and m ２１ Each of these is an integer between 0 and 5, and m ２２ m is an integer between 1 and 5. ２３ n is an integer between 0 and 5. ２１ [This is an integer between 1 and 15.]

[0021]

[0022] [In formula (3), *J ３１ Y ２１ This represents the bonding position with R ３１ and R ３２ Each independently represents a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, R ３１ and R ３２ They may be bonded together to form a ring, or R ３１ and R ３２ R ３１ and R ３２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ３３ ~R ３５ Each independently represents a cyano group, a C2-C30 alkyloxycarbonyl group which may have substituents, or a C1-C30 alkylsulfonyl group which may have substituents, X ３１ is an oxygen atom, a sulfur atom, or N-Q ３１ This represents Q ３１represents a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. ] <Hydrogen group A> A branched, linear or cyclic alkyl group having 1 to 30 carbon atoms, a branched, linear or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, linear or cyclic alkynyl group having 2 to 30 carbon atoms, in which part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group and / or a silicon atom.

[0023] Aspect 2 of the present invention is a polymer compound of aspect 1, wherein Y in formula (2) ２１ At least one of them is independently represented by the following formula (4), where n in formula (2) is ２１ If the number is 2 or more, the Y ２１ R inside ４１ and R ４２ is, other Y ２１ R included ４１ or R ４２ This relates to polymer compounds that may be linked together to form a ring.

[0024]

[0025] [In formula (4), R ４１ and R ４２ Each independently represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ４１ and R ４２ They may be joined together to form a ring.

[0026] A third aspect of the present invention is a polymer compound of the first or second aspect, wherein Y in formula (2) ２１ At least one of these is independently represented by the following formula (5), formula (6), or formula (7), provided that n in formula (2) is ２１ If the number is 2 or more, the Y ２１ R inside ５１ , R ５２ , R ６１ , R ６２ , and R７１ ~R ７７ is the R contained in other Y ２１ ５１ R ５２ R ６１ R ６２ or R ７１ ~R ７７ It relates to a polymer compound which may be linked to form a ring with R

[0027]

[0028] [In formula (5), R ５１ and R ５２ each independently represent a hydrogen atom, a group selected from the group of hydrocarbon groups A which may have a substituent, an aromatic group 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. Also, R ５１ and R ５２ may be bonded to form a ring. ]

[0029]

[0030] [In formula (6), R ６１ and R ６２ each independently represent a hydrogen atom, a group selected from the group of hydrocarbon groups A which may have a substituent, an aromatic group 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. Also, R ６１ and R ６２ may be bonded to form a ring, and X ６１ represents an oxygen atom, a sulfur atom or N-Q ６１ and Q ６１ represents a hydrogen atom, a group selected from the group of hydrocarbon groups A which may have a substituent, an aromatic group 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. ]

[0031]

[0032] [In formula (7), R​７１ ~R ７７ each independently represents a hydrogen atom, a group selected from the group A of hydrocarbon groups which may have a substituent, an aromatic group 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, and further, at least two of R ７１ ~R ７７ may be bonded to each other to form a ring. ]

[0033] Embodiment 4 of the present invention is a polymer compound according to any one of Embodiments 1 to 3, which contains a repeating unit represented by the formula (1-1), and R in the formula (1-1) １１１ is a methyl group, and R １１２ ~R １１３ are hydrogen atoms.

[0034] Embodiment 5 of the present invention is a polymer compound according to any one of Embodiments 1 to 4, which further contains a repeating unit represented by the following formula (8).

[0035]

[0036] [In the formula (8), R ８１ and R ８２ each independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, or a halogen atom, L ８１ each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from the group A of hydrocarbon groups 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, Y ８１ each independently represents a hydrogen atom, a group selected from the group A of hydrocarbon groups which may have a substituent, an aromatic group which may have a substituent, a heterocyclic group which may have a substituent, or a hydroxy group, and n ８１ is an integer of 0 to 10. ]

[0037] Embodiment 6 of the present invention is a polymer compound according to any one of Embodiments 1 to 5, which further contains a repeating unit represented by the following formula (9).

[0038]

[0039] [In formula (9), A ９１ A represents a trivalent group obtained by removing two hydrogen atoms from a group selected from the hydrocarbon group A, which may have substituents. ９２ Each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, and L ９１ Each independently represents a single bond, a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, R ９１ n represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, ９１ n is an integer between 0 and 5. ９２ [This is an integer between 0 and 1.]

[0040] Aspect 7 of the present invention is the polymer compound of Aspect 6, wherein A in formula (9) ９１ This relates to a polymer compound represented by the following formula (10).

[0041]

[0042] [In formula (10), R １０１ ~R １０３ Each of these independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom. *J １０１ is, L ９１ or R ９１ This indicates the bonding position with *J １０２ *J represents the connection position with adjacent repeating units. １０３ is, A ９２ This indicates the connection position with or with an adjacent repeating unit.

[0043] Embodiment 8 of the present invention relates to a polymer compound comprising, in any one of embodiments 1 to 7, a repeating unit represented by the following formula (11).

[0044]

[0045] [In formula (11), R １１１１ ~R １１１６ Each of these is independently a group selected from the hydrocarbon group A, which may have a hydrogen atom or a substituent, and L １１１１ and L １１１２ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, Y １１１１ and Y １１１２ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, a hydroxyl group which may have substituents, or a silyl group which may have substituents, and R １１１３ ~R １１１６ , L １１１１ and L １１１２ At least two of them may be joined together to form a ring, n １１１１ and n １１１２ Each of these is an integer between 0 and 5, independently of the others.

[0046] Aspect 9 of the present invention relates to a composition comprising one polymer compound from any one of aspects 1 to 8 and an organic solvent.

[0047] Aspect 10 of the present invention relates to a nonlinear optical element comprising a film containing one of the polymer compounds from aspects 1 to 8.

[0048] Aspect 11 of the present invention relates to a nonlinear optical element that operates based on the electro-optic effect, in the nonlinear optical element of Aspect 10.

[0049] Aspect 12 of the present invention relates to an optical modulator comprising a nonlinear optical element according to aspect 10 or 11.

[0050] The present invention provides a polymer compound with improved filterability and excellent thermal stability due to the suppression of viscosity increase and gelation during heating, and also provides a composition containing the polymer compound. Furthermore, the present invention provides a nonlinear optical element using the above composition, and provides an optical modulator equipped with the nonlinear optical element that operates based on the electro-optic effect.

[0051] <Explanation of Terms> The terms used in this specification are explained below.

[0052] <Polymer Compounds> In this specification, polymer compounds refer to compounds having a molecular weight of 2000 or more and containing four or more repeating units in the molecule. Polymer compounds are not particularly limited, but are preferably polymers, and may be homopolymers, block copolymers, random copolymers, alternating copolymers, or graft copolymers, or in other forms.

[0053] <Copolymer> A copolymer is a polymer compound that has two or more repeating units in its molecule.

[0054] <Substituents> Unless otherwise specified, substituents are any group, but preferably the substituent group W described below. １ The group is selected from the substituent group W. The substituents that may be present are also the substituent group W. １ If it is stated that selection from is preferable, the preferred substituents are also the substituent group W below. １ As stated therein.

[0055] <Substituent group W １ > Substituent group W １This group consists of hydroxyl groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aromatic oxy groups, aralkyloxy groups, alkylthio groups, aromatic thio groups, aralkylthio groups, alkyloxycarbonyl groups, dialkylamino groups, diarylamino groups, arylalkylamino groups, acyl groups, halogen atoms, haloalkyl groups, arylthio groups, silyl groups, siloxy groups, cyano groups, aralkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups. These substituents may include linear, branched, or cyclic structures.

[0056] Substituent group W １ More specifically, the following structures can be cited, from the [alkyl group] to the [bonding of adjacent substituents].

[0057] [Alkyl groups] Alkyl groups are linear, branched, or cyclic, and have one or more carbon atoms, preferably four or more, usually 24 or less, preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group, adamantyl group, etc.

[0058] [Alkenyl group] An alkenyl group is linear, branched, or cyclic, and usually has two or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include vinyl groups.

[0059] [Alkynyl group] The alkynyl group is linear or branched, usually has two or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include the ethynyl group.

[0060] [Alkyloxy Groups] Alkyloxy groups are linear, branched, or cyclic, have one or more carbon atoms, and usually have 24 or fewer carbon atoms, preferably 12 or fewer. Specific examples include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, dodecyloxy group, adamantyloxy group, etc.

[0061] [Aromatic oxy group] The aromatic oxy group has four or more carbon atoms, preferably five or more, and usually 36 or fewer, preferably 24 or fewer. Specific examples include the phenoxy group, naphthoxy group, and pyridyloxy group.

[0062] [Aralkyloxy group] The aralkyloxy group has four or more carbon atoms, preferably five or more, and is usually 50 or less, preferably 30 or less. Specific examples include benzyloxy group, tolylmethoxy group, thiophenylmethoxy group, 2-phenylethyloxy group, 2-phenylpropyl-2-yloxy group, 2-phenylbutyl-2-yloxy group, 3-phenylpentyl-3-yloxy group, 3-phenyl-1-propyloxy group, 4-phenyl-1-butyloxy group, 5-phenyl-1-pentyloxy group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, 8-phenyl-1-octyloxy group, and the like.

[0063] [Alkylthio group] An alkylthio group has one or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, n-hexylthio group, cyclohexylthio group, dodecylthio group, adamantylthio group, etc.

[0064] [Aromatic Thio Groups] Aromatic thio groups have three or more carbon atoms, preferably four or more, and usually 50 or fewer, preferably 30 or fewer. Specifically, examples include phenylthio groups, naphthylthio groups, pyridylthio groups, etc.

[0065] [Aralkylthio group] The aralkylthio group has four or more carbon atoms, usually 50 or less, preferably 30 or less. Specific examples include the benzylthio group, tolylmethylthio group, 2-phenylethylthio group, 2-phenylpropyl-2-ylthio group, 2-phenylbutyl-2-ylthio group, 3-phenylpentyl-3-ylthio group, 3-phenyl-1-propylthio group, 4-phenyl-1-butylthio group, 5-phenyl-1-pentylthio group, 6-phenyl-1-hexylthio group, 7-phenyl-1-heptylthio group, and 8-phenyl-1-octylthio group.

[0066] [Alkyloxycarbonyl group] The alkyloxycarbonyl group has two or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include the methoxycarbonyl group and the ethoxycarbonyl group.

[0067] [Dialkylamino group] A dialkylamino group has two or more carbon atoms, usually 24 or fewer, preferably 12 or fewer. Specific examples include dimethylamino group and diethylamino group.

[0068] [Amino Group] The amino group may have substituents, preferably a secondary amino group or a tertiary amino group, and more preferably a tertiary amino group. Preferred substituents on the amino group are alkyl groups, cycloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the amino group, they may be the same or different, and they may bond to each other to form a ring with the nitrogen atom to which each is bonded. Specific examples include dimethylamino group, diethylamino group, ethylmethylamino group, n-propylmethylamino group, di-iso-propylamino group, di-n-butylamino group, di-n-hexylamino group, methylphenylamino group, ethylphenylamino group, butylphenylamino group, hexylphenylamino group, diphenylamino group, 2,6-dimethylphenylphenylamino group, and 2,4,6-trimethylphenylphenylamino group.

[0069] [Halogen atoms] Halogen atoms are typically fluorine, chlorine, bromine, or iodine atoms. More preferably, they are fluorine atoms.

[0070] [Haloalkyl groups] Haloalkyl groups have one or more carbon atoms, usually 12 or fewer, preferably 6 or fewer. Specific examples include trifluoromethyl groups and chloromethyl groups, with trifluoromethyl groups being more preferred.

[0071] [Silicone group] A silyl group typically has two or more carbon atoms, preferably three or more, and typically 36 or fewer carbon atoms, preferably 24 or fewer. Specific examples include trimethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, etc.

[0072] [Siloxy group] The siloxy group has two or more carbon atoms, preferably three or more, and is usually 36 or less, preferably 24 or less, and more preferably 18 or less. Specific examples include the trimethylsiloxy group, tert-butyldimethylsiloxy group, tert-butyldiphenylsiloxy group, and triphenylsiloxy group.

[0073] [Aralkyl Groups] Aralkyl groups typically have 7 or more carbon atoms, preferably 9 or more, and typically 30 or less, preferably 18 or less, and more preferably 10 or less. Specific examples include benzyl group, 2-phenylethyl group, 2-phenylpropyl-2-yl group, 2-phenylbutyl-2-yl group, 3-phenylpentyl-3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, and 8-phenyl-1-octyl group. [Aromatic Hydrocarbon Groups] Aromatic hydrocarbon groups typically have 6 or more carbon atoms, and typically 36 or less, preferably 24 or less. Specific examples include phenyl group, naphthyl group, and groups in which multiple phenyl groups are linked together.

[0074] [Aromatic Heterocyclic Groups] Aromatic heterocyclic groups have three or more carbon atoms, preferably four or more, and usually 36 or fewer, preferably 24 or fewer. Specific examples of aromatic heterocyclic groups include thienyl groups and pyridyl groups.

[0075] [Shape of substituents] The substituents may include any of the following structures: linear, branched, or cyclic.

[0076] [Bonding of adjacent substituents] When the above substituents are adjacent, adjacent substituents may bond to each other to form a ring. Preferred ring sizes are four-membered rings, five-membered rings, and six-membered rings. Specific examples include cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0077] <Alkyl groups> Alkyl groups may have substituents, and may be linear, branched, or cyclic. While the number of carbon atoms is generally not limited, it is preferably between 1 and 30 carbon atoms, more preferably 20 carbon atoms or less, and even more preferably 10 carbon atoms or less. Specific examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, dodecyl, and adamantyl groups. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0078] <Aromatic Hydrocarbon Groups> Aromatic hydrocarbon groups refer to monovalent, divalent, or trivalent or more structures of hydrocarbon aromatic ring structures, depending on their bonding state within the structure of the compounds described below. The number of carbon atoms in an aromatic hydrocarbon group is not usually limited, but is preferably 6 to 60 carbon atoms, more preferably 48 carbon atoms or less, and even more preferably 30 carbon atoms or less. Specifically, examples include 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, fluorantene rings, and fluorene rings, or structures in which multiple groups selected from these are linked together. When multiple aromatic hydrocarbon groups are linked together, a structure with 2 to 10 linked groups is usually given, and a structure with 2 to 5 linked groups is preferred. When multiple aromatic hydrocarbon groups are linked together, the same structure may be linked, or different structures may be linked. The substituents that these groups may have are the substituent group W. １ Selected from.

[0079] <Aromatic Heterocyclic Groups> Aromatic heterocyclic groups refer to monovalent, divalent, or trivalent or more heteroaromatic ring structures, depending on their bonding state within the structure of the compounds described below. While the number of carbon atoms in an aromatic heterocyclic group is not usually limited, it is preferably between 3 and 50 carbon atoms, more preferably 45 carbon atoms or less, and even more preferably 30 carbon atoms or less. Specifically, examples include monocyclic rings with 5 to 6 members or fused ring groups containing 2 to 4 rings, such as furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienopyrrole rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinnoline rings, quinoxaline rings, phenanthridine rings, perimidine rings, quinazoline rings, and quinazolinone rings, or groups in which multiple such groups are linked. When multiple aromatic heterocyclic groups are linked, the same structure may be linked, or different structures may be linked. When multiple aromatic heterocyclic groups are linked, typically a structure with 2 to 10 linked groups is common, and a structure with 2 to 5 linked groups is preferred. The substituents that these groups may have are the substituent group W. １ Selected from: <Aromatic Group> The aromatic group may have substituents and represents the aforementioned aromatic hydrocarbon group or aromatic heterocyclic group, and refers to a monovalent, divalent, or trivalent or more structure depending on the bonding state in the structure of the compound that is the subject of the description below. The aromatic group may be a group in which multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, the same structure may be linked, or different structures may be linked. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, a structure in which 2 to 10 are linked together is usually given, and a structure in which 2 to 5 are linked together is preferred. The substituents that these groups may have are substituent group W １ Selected from.

[0080] <Amino Group> The amino group may have substituents, preferably a secondary amino group or a tertiary amino group, and more preferably a tertiary amino group. Preferred substituents on the amino group are groups selected from hydrocarbon group A or aromatic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the amino group, they may be the same or different, and they may be bonded to each other to form a ring with the nitrogen atom to which each is bonded. Specific examples include dimethylamino group, diethylamino group, ethylmethylamino group, n-propylmethylamino group, di-iso-propylamino group, di-n-butylamino group, di-n-hexylamino group, methylphenylamino group, ethylphenylamino group, butylphenylamino group, hexylphenylamino group, diphenylamino group, 2,6-dimethylphenylphenylamino group, and 2,4,6-trimethylphenylphenylamino group. The substituents that these groups may have are substituent group W. １ Selected from.

[0081] <Halogen atoms> Halogen atoms are typically fluorine, chlorine, bromine, or iodine atoms. More preferably, fluorine atoms.

[0082] <Alkyloxycarbonyl Group> The alkyloxycarbonyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 or more carbon atoms and 30 or less, more preferably 20 or less carbon atoms as the upper limit of the number of carbon atoms, and even more preferably 10 or less carbon atoms. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0083] <Alkylsulfonyl Group> Alkylsulfonyl groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 1 or more and 30 or less, more preferably 20 or less as the upper limit of the number of carbon atoms, and even more preferably 10 or less. Specific examples include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, dodecylsulfonyl group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0084] <Aralkyl Group> The aralkyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 20 carbon atoms or less. Specific examples include benzyl group, 2-phenylethyl group, 2-phenylpropyl-2-yl group, 2-phenylbutyl-2-yl group, 3-phenylpentyl-3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, 8-phenyl-1-octyl group, etc. The substituents that these groups may have are substituted group W. １ Selected from.

[0085] <Boryl Group> The boryl group may have substituents, preferably a secondary boryl group or a tertiary boryl group, and more preferably a tertiary boryl group. Preferred substituents on the boryl group are hydroxyl groups, alkyloxycarbonyl groups, alkyl groups, cycloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the boryl group, they may be the same or different, and they may be bonded to each other, forming a ring with the boron atom to which each is bonded. The substituents that these groups may have are substituted group W. １ Selected from.

[0086] <Acyl Group> The acyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 50 carbon atoms, more preferably 24 carbon atoms or less as the upper limit of the carbon number, and even more preferably 12 carbon atoms or less. Specific examples include the benzoyl group and the acetyl group. The substituents that these groups may have are the substituent group W. １ Selected from.

[0087] <Aromatic Oxy Group> The aromatic oxy group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 3 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the carbon number, and even more preferably 20 carbon atoms or less. Specific examples include naphthoxy groups and phenyloxy groups. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0088] <Aralkyloxy group> The aralkyloxy group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 4 or more carbon atoms and 50 or less, more preferably 30 or less carbon atoms as the upper limit of the carbon number, and even more preferably 20 or less carbon atoms. Specific examples include benzyloxy group, tolylmethoxy group, thiophenylmethoxy group, 2-phenylethyloxy group, 2-phenylpropyl-2-yloxy group, 2-phenylbutyl-2-yloxy group, 3-phenylpentyl-3-yloxy group, 3-phenyl-1-propyloxy group, 4-phenyl-1-butyloxy group, 5-phenyl-1-pentyloxyl group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, 8-phenyl-1-octyloxy group, etc. The substituents that these groups may have are substituted group W. １ Selected from.

[0089] <Aromatic Thio Group> The aromatic thio group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 3 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the carbon number, and even more preferably 20 carbon atoms or less. Specific examples include naphthylthio group, tolylthio group, phenylthio group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0090] <Aalkylthio group> The aralkylthio group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 4 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 20 carbon atoms or less. Specific examples include benzylthio group, tolylmethylthio group, 2-phenylethylthio group, 2-phenylpropyl-2-ylthio group, 2-phenylbutyl-2-ylthio group, 3-phenylpentyl-3-ylthio group, 3-phenyl-1-propylthio group, 4-phenyl-1-butylthio group, 5-phenyl-1-pentylthio group, 6-phenyl-1-hexylthio group, 7-phenyl-1-heptylthio group, 8-phenyl-1-octylthio group, etc. The substituents that these groups may have are grouped W. １ Selected from.

[0091] <Hydrogen Ring Group> A hydrocarbon ring group is a cyclic hydrocarbon group that may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 or more and 50 or less, more preferably 20 or less as the upper limit of the number of carbon atoms, and even more preferably 10 or less. Specific examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, or groups formed by linking multiple of these groups. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0092] <Hydrogen Group A> Hydrocarbon Group A refers to branched, linear, or cyclic alkyl groups having 1 to 30 carbon atoms, branched, linear, or cyclic alkenyl groups having 2 to 30 carbon atoms, or branched, linear, or cyclic alkynyl groups having 2 to 30 carbon atoms, where a portion of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom. From the standpoint of compound stability, when a portion of the carbon atoms is substituted with an oxygen atom or a sulfur atom, it is preferable that they are bonded to the surrounding carbon atoms by a single bond. Specifically, the following groups can be listed.

[0093] Specific examples of unsubstituted hydrocarbon group A are hydrocarbon chains having 1 to 15 carbon atoms, more specifically, methyl group, ethyl group, 1-butyl group, tert-butyl group, cyclopentyl group, 4-ethyl-1-cyclohexyl group, 2-penten-1-yl group, 1-octyl group, 1-decyl group, etc., with methyl group, ethyl group, and 1-butyl group being preferred. Specific examples of hydrocarbon group A, in which part of the carbon chain is substituted with an oxygen atom, include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, dodecyloxy group, 2-ethoxyethyl group, 2-(2-ethoxyethoxy)ethyl group, 2-hydroxyethyl group, tetrahydropyranyloxypropyl group, and the like, with 2-ethoxyethyl group and 2-hydroxyethyl group being preferred, and 2-hydroxyethyl group being particularly preferred. Specific examples of hydrocarbon group A in which part of the carbon chain is substituted with a sulfur atom include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, n-hexylthio group, cyclohexylthio group, dodecylthio group, 2-ethylthioethyl group, tetrahydrothienyl group, and 2-(2-ethylthioethylthio)ethyl group. Specific examples of cases where part of the carbon chain is substituted with an aromatic hydrocarbon group include benzyl group, phenylethyl group, phenylhexyl group, 4-phenylcyclohexylmethyl group, and 4-methylbenzyl group. Specific examples of hydrocarbon group A in which part of the carbon chain is substituted with a silicon atom include trimethylsilyl group, triethylsilyl group, propyldimethylsilyl group, tert-butyldimethylsilyl group, and tert-butyldiphenylsilyl group.Furthermore, a portion of the carbon chain may be simultaneously substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group and / or a silicon atom, and more preferably simultaneously substituted with an oxygen atom and a silicon atom. Specific examples of such hydrocarbon group A include 2-(trimethylsilyloxy)ethyl group, 2-(tert-butyldimethylsilyloxy)ethyl group, 4-(tert-butyldimethylsilyloxy)butyl group, 2-(tert-butyldiphenylsilyloxy)ethyl group, 2-(tert-butyldimethylsilyloxy)hexyl group, and 2-(tert-butyldiphenylsilyloxy)ethyl group, and preferably 2-(tert-butyldimethylsilyloxy)ethyl group, 4-(tert-butyldimethylsilyloxy)butyl group, and 2-(tert-butyldiphenylsilyloxy)ethyl group. Substituents that these groups may have are substituent group W. １ Selected from, preferably a hydroxyl group, a halogen atom, or a cyano group, more preferably a hydroxyl group, a halogen atom, or a cyano group, more preferably a hydroxyl group, a halogen atom, or a cyano group, more preferably a hydroxyl group, a halogen atom, or a hydroxyl group.

[0094] <Heterocyclic Groups> Heterocyclic groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 or more and 50 or less, more preferably 20 or less as the upper limit of the number of carbon atoms, and even more preferably 10 or less. Specific examples include thiane group, 1,4-dithiane group, tetrahydrofuran group, tetrahydropyran group, pyran group, 1,4-dioxane group, or groups formed by linking multiple of these groups. The substituents that these groups may have are the substituent group W １ Selected from.

[0095] <π-conjugated linkage group> A π-conjugated linkage group is a divalent group in the structure of a compound described below, consisting of alternating single and multiple bonds and possessing delocalized electrons (π electrons). A π-conjugated linkage group may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 2 to 50 carbon atoms, more preferably 30 carbon atoms or less, and even more preferably 20 carbon atoms or less. Furthermore, substituents on multiple π-conjugated linkage groups may bond together to form a cyclic structure. Specific examples include divalent groups consisting of vinylene groups, phenylene groups, thiophene rings, furan rings, or pyrrole rings, or groups formed by linking multiple such groups. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0096] <Nonlinear Optical Materials> In this specification, "nonlinear optical materials" refers to nonlinear optically active compounds, nonlinear optically active polymer compounds, or both.

[0097] <Nonlinear Optically Active Compounds> In this specification, a nonlinear optically active compound refers to a compound with a molecular weight of less than 2000 that exhibits nonlinear optical activity. Nonlinear optically active compounds include compounds represented by formula (2).

[0098] <Nonlinear Optically Active Polymer Compounds> In this specification, a nonlinear optically active polymer compound refers to a polymer compound that exhibits nonlinear optical activity, and nonlinear optically active polymer compounds include polymer compounds that contain at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3). When referring to a polymer compound that contains at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3), with particular attention to its nonlinear optical activity, it shall be expressed as a nonlinear optically active polymer compound containing at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3). Furthermore, in this specification, among nonlinear optically active polymer compounds, polymer compounds that do not contain repeating units represented by formula (1-1), formula (1-2), and formula (1-3) are referred to as nonlinear optically active polymer compounds that do not have repeating units represented by formula (1-1), formula (1-2), and formula (1-3).

[0099] In this specification, the solids of a composition refer to the components other than the solvent contained in the composition, and even if the components other than the solvent are liquid at room temperature, they are included in the solids.

[0100] Embodiments of the present invention will be described in detail below.

[0101] <Polymer Compounds> The polymer compounds according to the embodiments of the present invention include at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3), which will be described later.

[0102] <Polymer compound containing repeating units represented by formula (1-1)> In one embodiment, the polymer compound in this embodiment contains repeating units represented by formula (1-1). In addition to the above repeating units, the polymer compound in this embodiment may also contain at least one selected from the group consisting of repeating units represented by formula (1-2) and repeating units represented by formula (1-3), which will be described later.

[0103]

[0104] [In formula (1-1), R １１１ ~R １１３ Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom, L １１１ and L １１２ Each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A above, which may have substituents, and X １１１ Y is a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), １１１ and Y １１２ Each of these is an oxygen atom or N-Z １１１ Z １１１ n is a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic hydrocarbon group which may have substituents, or an aromatic heterocyclic group which may have substituents, １１１ [This represents values ​​between 0 and 1.]

[0105] [R １１１ ~R １１３ ] R １１１ ~R １１３ Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom. Specific examples of linear alkyl groups having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. The substituents that the linear alkyl group having 1 to 5 carbon atoms may have are preferably halogen atoms, more preferably fluorine atoms or chlorine atoms, and even more preferably fluorine atoms, from the viewpoint of the durability of the compound.

[0106] Specific examples of the halogen atom are a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of improving the non-linear optical effect, a fluorine atom and a chlorine atom are preferred, and a fluorine atom is more preferred.

[0107] In terms of the stability of the compound, R １１１ ~ R １１３ is preferably a hydrogen atom or a methyl group, R １１１ is a hydrogen atom or a methyl group, and R １１２ and R １１３ being a hydrogen atom is more preferred, and R １１１ being a methyl group and R １１２ and R １１３ being a hydrogen atom is particularly preferred.

[0108] [L １１１ 、L １１２ L １１１ and L １１２ are each independently a divalent group obtained by removing one hydrogen atom from a group selected from the above hydrocarbon group A which may have a substituent. The divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have a substituent is synonymous with the description given in the explanation of the above terms. From the viewpoint of improving durability, L １１１ and L １１２ are preferably a divalent alkyl group having 1 to 10 carbon atoms, more preferably a divalent alkyl group having 1 to 5 carbon atoms, still more preferably a divalent alkyl group having 1 to 3 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0109] [X １１１ X １１１ is a group obtained by removing one hydrogen atom from a compound represented by the following formula (2).

[0110] [Y １１１ 、Y １１２ Y １１１ and Y １１２ are each independently an oxygen atom or N-Z １１１ . Y １１１ and Y １１２ being an oxygen atom is preferred from the viewpoint of solubility.

[0111] [Z１１１ Z １１１ is a hydrogen atom, a group selected from the above hydrocarbon group A which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. The group selected from the hydrocarbon group A which may have a substituent is synonymous with the description given in the explanation of the above terms. The aromatic group which may have a substituent is synonymous with the description given in the explanation of the above terms. The heterocyclic group which may have a substituent is synonymous with the description given in the explanation of the above terms. From the viewpoint of the thermal durability of the compound, Z １１１ is preferably a hydrogen atom.

[0112] [n １１１ n １１１ represents 0 to 1.

[0113] [Substituent] These R １１１ to R １１３ , L １１１ , L １１２ and Z １１１ may have a substituent which, unless otherwise specified, is synonymous with the substituent which each of the groups described in the explanation of the above terms may have, and is preferably a group selected from the above substituent group W １ selected from.

[0114] <Polymer compound containing a repeating unit represented by formula (1-2)> The polymer compound in the present embodiment, as one aspect, contains a repeating unit represented by formula (1-2). The polymer compound in the present embodiment may contain at least one selected from the group consisting of the repeating unit represented by the above formula (1-1) and the repeating unit represented by formula (1-3) described later in addition to the above repeating unit. By containing the repeating unit represented by the following formula (1-2), it exhibits non-linear optical activity, has excellent thermal stability, shows a relatively high glass transition temperature (Tg), and when formed into a film, the vulnerability of the film tends to be improved.

[0115]

[0116] [In formula (1-2), R １２１ and R １２２Each independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom, L １２１ Each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, or a divalent aromatic group which may have substituents, X １２１ n is a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), and n １２１ [This is an integer between 1 and 5.]

[0117] [R １２１ , R １２２ ] R １２１ and R １２２ Each is independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom. The definition of alkyl group is the same as that given in the explanation of the terms above. Specific examples of halogen atoms are fluorine, chlorine, and bromine atoms. From the viewpoint of improving nonlinear optical effects, fluorine and chlorine atoms are preferred, and fluorine atoms are more preferred. From the viewpoint of manufacturing stability, R １２１ and R １２２ Each of these is preferably a hydrogen atom or a methyl group, R １２１ is a hydrogen atom, R １２２ It is more preferable that R is a hydrogen atom or a methyl group. １２１ and R １２２ It is most preferable that both are hydrogen atoms.

[0118] [L １２１ ] L １２１ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, or a divalent aromatic group, which may have substituents. The group selected from hydrocarbon group A, which may have substituents, is defined in the same way as described in the explanation of the terms above. The aromatic group, which may have substituents, is defined in the same way as described in the explanation of the terms above. The heterocyclic group, which may have substituents, is defined in the same way as described in the explanation of the terms above. From the viewpoint of improving the durability of the compound, L １２１The group is preferably a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A which may have substituents, a phenylene group, more preferably a branched, chain, or cyclic divalent alkyl group having 1 to 20 carbon atoms which may have substituents, a phenylene group, even more preferably a branched, chain, or cyclic divalent alkyl group having 1 to 10 carbon atoms which may have substituents, a phenylene group, a particularly preferred chain divalent alkyl group having 1 to 10 carbon atoms which is phenylene, and most preferably an ethylene group.

[0119] [X １２１ ] X １２１ This is a group obtained by removing one hydrogen atom from the compound represented by the following formula (2).

[0120] [n １２１ ] n １２１ n is an integer from 1 to 5. From the standpoint of compound stability, １２１ 1 is preferable.

[0121] [Substituent] L １２１ Unless otherwise specified, the optional substituents are synonymous with the optional substituents of each substituent described in the preceding explanation of the terms.

[0122] <Polymer compound containing repeating units represented by formula (1-3)> In one embodiment, the polymer compound in this embodiment contains repeating units represented by formula (1-3). In addition to the above repeating units, the polymer compound in this embodiment may also contain at least one selected from the group consisting of repeating units represented by formula (1-1) and repeating units represented by formula (1-2).

[0123]

[0124] [In formula (1-3), R １３１ ~R １３３ Each independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom, R １３４ Each of these is independently a group selected from hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, n １３２ If the number is 2 or more, the R １３４ is another R１３４ It may also be bonded to form a ring, R １３５ Each is independently a single bond, an optionally substituted divalent alkyl group, an optionally substituted divalent aromatic group, or an optionally substituted divalent aralkyl group, X １３１ Each of these is independently a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), n １３１ n is an integer between 1 and 5. １３２ n is an integer between 0 and 4, where n １３１ to n １３２ The sum of the numbers is 5 or less.

[0125] [R １３１ ~R １３３ ] R １３１ ~R １３３ Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom. Specific examples of linear alkyl groups having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. The substituents that the linear alkyl group having 1 to 5 carbon atoms may have are preferably halogen atoms, more preferably fluorine atoms or chlorine atoms, and even more preferably fluorine atoms, from the viewpoint of the durability of the compound.

[0126] Specific examples of halogen atoms include fluorine, chlorine, and bromine atoms. From the viewpoint of improving nonlinear optical effects, fluorine and chlorine atoms are preferred, and fluorine atoms are more preferred.

[0127] From the standpoint of compound stability, R １３１ ~R １３３ R is preferably a hydrogen atom or a methyl group. １３１ is a hydrogen atom or a methyl group, R １３２ and R １３３ It is more preferable that R is a hydrogen atom. １３１ ~R １３３ It is particularly preferable that the atom is a hydrogen atom.

[0128] [R １３４ ] R １３４Each of these is independently a group selected from hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, n １３２ If the number is 2 or more, the R １３４ is another R １３４ It may also be bonded to form a ring. １３２ If R is 1 or greater, from the viewpoint of compound stability, １３４ It is preferably a group selected from hydrocarbon group A, and more preferably a branched, chain-like, or cyclic alkyl group having 1 to 30 carbon atoms.

[0129] [R １３５ ] R １３５ Each of these is independently a single bond, an optionally substituted divalent alkyl group, an optionally substituted divalent aromatic group, or an optionally substituted divalent aralkyl group. From the viewpoint of improving manufacturability, R １３５ It is preferably a group selected from hydrocarbon group A, or a single bond, more preferably a branched, chain-like, or cyclic alkyl group having 1 to 30 carbon atoms, or a single bond, and particularly preferably a single bond. Furthermore, from the viewpoint of improving the durability of the compound, R is added to the main chain of the polymer compound. １３５ It is preferable that it is located at the m position or the p position, and more preferably at the p position.

[0130] [X １３１ ] X １３１ Each of these groups is independently a group obtained by removing one hydrogen atom from the compound represented by the following formula (2).

[0131] [n １３１ ] n １３１ n is an integer from 1 to 5. From the standpoint of solubility, １３１ The value is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

[0132] [n １３２ ] n １３２ n is an integer between 0 and 4. From the viewpoint of the stability of the compound, １３２ n is preferably 0 to 3, more preferably 0 or 1, and particularly preferably 0. However, １３１ to n １３２The sum of the numbers is 5 or less.

[0133] [Substituents] These R １３１ ~R １３５ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the explanation of the terms above, and preferably the substituent group W １ It is a base selected from among them.

[0134] <Equation (2)> X in Equation (1-1) １１１ , X in equation (1-2) １２１ , and X in equation (1-3) １３１ These are groups obtained by removing one hydrogen atom from the compound represented by formula (2) below. Note that the compounds represented by formula (2) below are independent of each other in formulas (1-1) to (1-3), and may be the same or different.

[0135]

[0136] [In formula (2), Ar ２１ Each of these is independently a divalent aromatic group which may have substituents, and R ２１ and R ２３ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, or a divalent aromatic group which may have substituents, and R ２２ and R ２４ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ２１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ２１ This is a group represented by the following formula (3), and m ２１ Each of these is an integer between 0 and 5, and m ２２ m is an integer between 1 and 5. ２３ n is an integer between 0 and 5. ２１ [This is an integer between 1 and 15.]

[0137] [Ar ２１ ] Ar ２１Each of these is independently a divalent aromatic group which may have substituents. The term "divalent aromatic group which may have substituents" is synonymous with the description given in the previous explanation of the terms. Ar ２１ The group is preferably a divalent group consisting of a benzene ring, a naphthalene ring, a 9,9-dialkylfluorene ring, a thiophene ring, or a biphenyl ring, and more preferably a divalent group consisting of a benzene ring, and these groups may have substituents.

[0138] [R ２１ , R ２３ ] R ２１ and R ２３ Each is independently a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, or a divalent aromatic group, which may have substituents. A divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, is synonymous with the description given in the explanation of the terms above. A divalent aromatic group, which may have substituents, is synonymous with the description given in the explanation of the terms above. From the viewpoint of film formation, R ２１ and R ２３ Preferably, R is a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have a benzene ring, a naphthalene ring, or substituents having 10 or fewer carbon atoms, and more preferably, a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have a benzene ring, or substituents having 5 or fewer carbon atoms. Also, from the viewpoint of solubility, ２１ and R ２３ They may be the same or different, but it is preferable that they be different.

[0139] [R ２２ , R ２４ ] R ２２ and R ２４Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom. A group selected from hydrocarbon group A which may have substituents is synonymous with the description given in the explanation of the terms above. An aromatic group which may have substituents is synonymous with the description given in the explanation of the terms above. An amino group which may have substituents is synonymous with the description given in the explanation of the terms above. A halogen atom is synonymous with the description given in the explanation of the terms above. From the viewpoint of improving nonlinear optical properties, R ２２ and R ２４ The group is preferably a group selected from hydrocarbon group A, which may have substituents, or an amino group, more preferably a group selected from hydrocarbon group A having 1 to 20 carbon atoms, which may have substituents, or an amino group, and is particularly preferably a linear alkyl group having 1 to 5 carbon atoms, which may be substituted, an ethoxy group, or an tertiary amino group, which may be substituted.

[0140] [Y ２１ ] Y ２１ Each of these is independently a divalent π-conjugated linkage group which may have substituents. ２１ If there are multiple Y ２１ The structures may be the same or different. Also, Y ２１ Multiple substituents on the compound may form bonds to create a cyclic structure. The term π-conjugated linkage is synonymous with the description given in the explanation of the terms above.

[0141] [Z ２１ ] Z ２１ This is the base represented by equation (3) described later.

[0142] [Substituents] These Ar ２１ , R ２１ ~R ２４ and Y ２１ Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group as described in the explanations of the terms above.

[0143] [subscript m ２１, m ２２ , m ２３ , n ２１ , m ２１ is, independently of each other, an integer from 0 to 5, and m ２２ is an integer from 1 to 5, and m ２３ is an integer from 0 to 5, and n ２１ is an integer from 1 to 15. From the viewpoint of improving the non-linear optical properties of the dye, m ２１ is preferably an integer from 0 to 4, more preferably an integer from 0 to 3, and even more preferably an integer from 0 to 2. m ２２ is preferably an integer from 1 to 4, more preferably an integer from 1 to 3. m ２３ is preferably an integer from 0 to 4, more preferably an integer from 0 to 3, and even more preferably an integer from 0 to 2. Also, n ２１ is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Also, from the viewpoint of reducing absorption loss, 14 or less is preferable, 13 or less is more preferable, and 10 or less is even more preferable.

[0144] <Formula (3)>

[0145]

[0146] [In Formula (3), *J ３１ represents the bonding position with Y, and R ２１ and R ３１ and R ３２ each independently represent a group selected from the hydrocarbon group A which may have a substituent, or an aromatic group which may have a substituent. R ３１ and R ３２ may combine to form a ring, or R ３１ and R ３２ may form a carbonyl group together with R ３１ and R ３２ and the carbon atom to which they are bonded. R ３３ to R ３５ each independently represent a cyano group, an alkyloxycarbonyl group having 2 to 30 carbon atoms which may have a substituent, or an alkylsulfonyl group having 1 to 30 carbon atoms which may have a substituent. X ３１ is an oxygen atom, a sulfur atom or N-Q３１ This represents Q ３１ This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents.

[0147] [*J ３１ ] *J ３１ Y ２１ This indicates the connection point with [the other element].

[0148] [R ３１ , R ３２ ] R ３１ and R ３２ Each independently represents a group selected from hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, and R ３１ and R ３２ They may be bonded together to form a ring, or R ３１ and R ３２ R ３１ and R ３２ These may form a carbonyl group together with the carbon atom to which they are bonded. Groups selected from hydrocarbon group A, which may have substituents, are described in the same way as described in the explanation of the terms above. Aromatic groups, which may have substituents, are described in the same way as described in the explanation of the terms above. From the viewpoint of film formation, R ３１ and R ３２ The R is preferably a group selected from group A of hydrocarbon groups with 1 to 20 carbon atoms, which may have substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may be substituted, with methyl, ethyl, linear or branched propyl, phenyl, and naphthyl groups being particularly preferred, and methyl and phenyl groups being the most preferred. ３１ and R ３２ The substituents that may be present are the substituent group W. １ It is preferable to select from the following, with alkyl groups and halogen atoms being more preferable, and fluorine atoms being most preferable.

[0149] [R ３３ ~R ３５ ] R ３３ ~R ３５Each of these independently represents a cyano group, an alkyloxycarbonyl group having 2 to 30 carbon atoms that may have substituents, or an alkylsulfonyl group having 1 to 30 carbon atoms that may have substituents. The alkyloxycarbonyl group having 2 to 30 carbon atoms that may have substituents is synonymous with the description given in the explanation of the terms above. The alkylsulfonyl group having 1 to 30 carbon atoms that may have substituents is synonymous with the description given in the explanation of the terms above. From the viewpoint of improving nonlinear optical properties, R ３３ ~R ３５ The group is preferably a cyano group, a C2-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents, with the cyano group being more preferred.

[0150] [X ３１ ] X ３１ is an oxygen atom, a sulfur atom, or N-Q ３１ It represents.

[0151] [Q ３１ ] Q ３１ This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. A group selected from hydrocarbon group A which may have substituents is synonymous with the description given in the explanation of the terms above. An aralkyl group which may have substituents is synonymous with the description given in the explanation of the terms above. From the viewpoint of film formation, a group selected from hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents is preferred, an aralkyl group which may have substituents is more preferred, and an aralkyl group which may have substituents is particularly preferred.

[0152] [Substituents] These R ３１ ~R ３５ and Q ３１ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the above-mentioned explanations, and preferably the substituent group W １ It is a base selected from among them.

[0153] <Preferred form 1 of formula (2)> Y in formula (2)２１ Preferably, at least one of them is independently represented by formula (4), provided that n in formula (2) ２１ If it is 2 or more, Y ２１ R inside ４１ and R ４２ is, other Y ２１ R included ４１ or R ４２ They may be connected to form a ring. When they are connected to form a ring, R ４１ and R ４２ Either of them may be a single bond.

[0154] <Formula (4)>

[0155]

[0156] [In formula (4), R ４１ and R ４２ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ４１ and R ４２ They may be joined together to form a ring.

[0157] [R ４１ , R ４２ ] R ４１ and R ４２ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group. A group selected from hydrocarbon group A which may have substituents is synonymous with the description given in the explanation of the terms above. An aromatic group which may have substituents is synonymous with the description given in the explanation of the terms above. An amino group which may have substituents is synonymous with the description given in the explanation of the terms above. A halogen atom is synonymous with the description given in the explanation of the terms above. A optionally substituted boryl group is synonymous with the description given in the explanation of the terms above. Also, R ４１and R ４２ They may be bonded together to form a ring. ４１ and R ４２ When they bond to form a ring, R ４１ and R ４２ Any of them may be a single bond. ４１ and R ４２ The relationship can be either a cis-field or a trans-field.

[0158] [Substituents] These R ４１ and R ４２ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the above-mentioned explanations, and preferably the substituent group W １ It is a base selected from among them.

[0159] <Preferred form 2 of formula (2)> Y in formula (2) ２１ Preferably, at least one of these is independently represented by the following formula (5), formula (6), or formula (7), provided that n in formula (2) ２１ If it is 2 or more, Y ２１ R inside ５１ , R ５２ , R ６１ , R ６２ , and R ７１ ~R ７７ is, other Y ２１ R included ５１ , R ５２ , R ６１ , R ６２ , or R ７１ ~R ７７ They may be connected to form a ring. When they are connected to form a ring, R ５１ , R ５２ , R ６１ , R ６２ and R ７１ ~R ７７ Either of them may be a single bond.

[0160] <Formula (5)>

[0161]

[0162] [In formula (5), R ５１ and R ５２Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ５１ and R ５２ They may be joined together to form a ring.

[0163] [R ５１ , R ５２ ] R ５１ and R ５２ R in equation (4) ４１ and R ４２ This is synonymous with R. From the viewpoint of improving the nonlinear optical effect, preferably R ５１ and R ５２ is a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0164] <Formula (6)>

[0165]

[0166] [In formula (6), R ６１ and R ６２ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ６１ and R ６２ They may be joined together to form a ring, X ６１ is an oxygen atom, a sulfur atom, or N-Q ６１ This represents Q ６１ This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group.

[0167] [R ６１ , R ６２ ] R６１ and R ６２ R in equation (4) ４１ and R ４２ This is synonymous with R. From the viewpoint of improving the nonlinear optical effect, preferably R ６１ and R ６２ is a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, more preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom.

[0168] [X ６１ ] X ６１ is an oxygen atom, a sulfur atom, or N-Q ６１ This represents a sulfur atom, preferably, from the viewpoint of improving nonlinear optical effects.

[0169] [Q ６１ ] Q ６１ This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or an aromatic group which may have substituents. A group selected from hydrocarbon group A which may have substituents is synonymous with the description given in the explanation of the terms above. An aromatic group which may have substituents is synonymous with the description given in the explanation of the terms above. From the viewpoint of film formation, a group selected from hydrocarbon group A with 1 to 20 carbon atoms which may have substituents, and an aromatic hydrocarbon group having 6 to 60 carbon atoms are preferred, a group selected from hydrocarbon group A with 1 to 20 carbon atoms which may have substituents, and an aromatic hydrocarbon group having 6 to 30 carbon atoms are more preferred, and a group selected from hydrocarbon group A with 1 to 10 carbon atoms which may have substituents, and an aromatic hydrocarbon group having 6 to 20 carbon atoms are particularly preferred.

[0170] [Substituent] Q ６１ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the above-mentioned explanations, and preferably the substituent group W １ It is a base selected from among them.

[0171] <Formula (7)>

[0172]

[0173] [In formula (7), R ７１ ~R ７７ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ７１ ~R ７７ At least two of them may be joined together to form a ring.

[0174] [R ７１ ~R ７７ ] R ７１ ~R ７７ R in equation (4) ４１ and R ４２ It is synonymous with R. ７１ ~R ７７ At least two of them may be bonded together to form a ring. From the viewpoint of improving the nonlinear optical effect, preferably R ７１ R is a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. ７２ ~R ７７ is a hydrogen atom, may have substituents, or is a group selected from hydrocarbon group A. More preferably, R ７１ R is a hydrogen atom or a group selected from hydrocarbon group A, which may have a substituent, ７２ , R ７３ , R ７６ and R ７７ is a hydrogen atom, and R ７４ and R ７５ is a hydrogen atom or a group selected from hydrocarbon group A, which may have a substituent. Most preferably, R ７１ R is a hydrogen atom or a group selected from hydrocarbon group A, which may have a substituent, ７２ , R ７３ , R ７６ and R ７７ is a hydrogen atom, and R ７４ and R ７５is a hydrogen atom or an alkyl group.

[0175] [Substituents] These R ７２ ~R ７７ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the explanation of the terms above, and preferably the substituent group W １ It is a base selected from among them.

[0176] <Further Repeating Units> The polymer compounds according to the embodiments of the present invention may further contain repeating units other than those described above. There are no particular restrictions on the further repeating units that may be included, but examples include repeating units represented by the following formulas (8), (9), or (11).

[0177] <Formula (8)> The polymer compound according to the embodiment of the present invention may further contain repeating units represented by the following formula (8). Furthermore, it is preferable that the polymer compound according to the embodiment of the present invention contains at least one selected from the group consisting of repeating units represented by formula (1-2) and repeating units represented by formula (1-3), and further contains repeating units represented by the following formula (8).

[0178]

[0179] [In formula (8), R ８１ and R ８２ Each independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom, L ８１ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, Y ８１ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a heterocyclic group which may have substituents, or a hydroxyl group, n ８１ [This is an integer between 0 and 10.]

[0180] [R８１ , R ８２ ] R ８１ and R ８２ R in equation (1-2) is １２１ and R １２２ It is synonymous with [the above].

[0181] [L ８１ ] L ８１ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents. The group selected from the hydrocarbon group A which may have substituents is defined in the same way as described in the explanation of the terms above. The aromatic group which may have substituents is defined in the same way as described in the explanation of the terms above. The heterocyclic group which may have substituents is defined in the same way as described in the explanation of the terms above. From the viewpoint of improving the durability of the compound, L ８１ The group is preferably a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A which may have substituents, a phenylene group, more preferably a branched, chain-like, or cyclic divalent alkyl group having 1 to 20 carbon atoms which may have substituents, a phenylene group which may have substituents, a branched, chain-like, or cyclic divalent alkyl group having 1 to 10 carbon atoms which may have substituents, a phenylene group which may have substituents, and a chain-like divalent alkyl group having 1 to 5 carbon atoms which is particularly preferred.

[0182] [Y ８１ ] Y ８１ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a heterocyclic group which may have substituents, or a hydroxyl group.

[0183] [Substituent] R ８１ , R ８２ , L ８１ , Y ８１ Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present in each substituent described in the preceding explanation of the terms.

[0184] [subscript n] ８１ ] n ８１n is an integer between 0 and 10. From the standpoint of compound stability, n ８１ The value is preferably 0 to 5, more preferably 0 to 2, particularly preferably 0 to 1, and most preferably 0.

[0185] <Formula (9)> The polymer compound according to the embodiment of the present invention may further contain a repeating unit represented by the following formula (9). Furthermore, it is preferable that the polymer compound according to the embodiment of the present invention contains at least one selected from the group consisting of repeating units represented by formulas (1-2) and repeating units represented by formulas (1-3), and further contains a repeating unit represented by the following formula (9).

[0186]

[0187] [In formula (9), A ９１ This represents a trivalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A, which may have substituents. ９２ Each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, and L ９１ Each independently represents a single bond, a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, R ９１ n represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents. ９１ n is an integer between 0 and 5. ９２ [This is an integer between 0 and 1.]

[0188] [A ９１ ] A ９１This represents a trivalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A, which may have substituents. From the viewpoint of compound stability, a trivalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A having 1 to 10 carbon atoms is preferred, a trivalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A having 1 to 5 carbon atoms is more preferred, a trivalent group obtained by removing two hydrogen atoms from an alkyl group having 1 to 5 carbon atoms is particularly preferred, and a trivalent group obtained by removing two hydrogen atoms from an alkyl group having 1 to 2 carbon atoms is most preferred.

[0189] [A ９２ ] A ９２ Each of these independently represents a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents. From the viewpoint of compound stability, a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A having 1 to 5 carbon atoms, which may have substituents, is preferred.

[0190] [L ９１ ] L ９１ Each of these independently represents a single bond, a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents. From the viewpoint of compound stability, a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A which may have substituents, an oxygen atom, a carbonyl group which may have substituents is preferred, a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A which may have substituents, an oxygen atom, a carbonyl group which is more preferred, and an alkyl group having 1 to 10 carbon atoms, an oxygen atom, or a carbonyl group which is particularly preferred.

[0191] [R ９１ ] R ９１This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents. From the viewpoint of compound stability, a group selected from hydrocarbon group A which may have substituents or an aromatic group which may have substituents is preferred, a group selected from hydrocarbon group A which may have substituents or a phenyl group which may have substituents is more preferred, and an alkyl group having 1 to 20 carbon atoms which may have substituents or a phenyl group which may have substituents is particularly preferred.

[0192] [Substituents] These A ９１ ~A ９２ , L ９１ and R ９１ Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group as described in the explanations of the terms above.

[0193] [subscript n] ９１ ] n ９１ is an integer between 0 and 5. From the standpoint of compound stability, 0 to 3 is preferred.

[0194] [subscript n] ９２ ] n ９２ is an integer between 0 and 1. From the standpoint of compound stability, it is preferably 0.

[0195] <Preferred form of formula (9)> The polymer compound according to the embodiment of the present invention is A in formula (9) ９１ It is preferable that this is represented by the following formula (10).

[0196]

[0197] [In formula (10), R １０１ ~R １０３ Each of these independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom. *J １０１ is, L ９１ or R ９１ This indicates the bonding position with *J １０２ *J represents the connection position with adjacent repeating units. １０３ is, A ９２This indicates the connection position with or with an adjacent repeating unit.

[0198] [R １０１ ~R １０３ ] R １０１ ~R １０３ Each of these independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom. From the viewpoint of the thermal durability of the compound, R １０１ R is preferably a linear alkyl group having 1 to 5 carbon atoms, which may have a hydrogen atom or substituents, and more preferably a hydrogen atom or a methyl group. Also, from the viewpoint of the heat resistance of the compound, １０２ , R １０３ It is preferable that it be a hydrogen atom.

[0199] [Substituents] These R １０１ ~R １０３ Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group as described in the explanations of the terms above.

[0200] [*J １０１ ~*J １０３ ] *J １０１ is, L ９１ or R ９１ This indicates the connection position with *J １０２ This indicates the connection position with adjacent repeating units. *J １０３ is, A ９２ This indicates the connection point with or with an adjacent repeating unit.

[0201] <Formula (11)> The polymer compound according to the embodiment of the present invention may further contain a repeating unit represented by the following formula (11).

[0202]

[0203] [In formula (11), R １１１１ ~R １１１６ Each of these is independently a group selected from the hydrocarbon group A, which may have a hydrogen atom or a substituent, and L １１１１ and L １１１２Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, Y １１１１ and Y １１１２ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, a hydroxyl group which may have substituents, or a silyl group which may have substituents, and R １１１３ ~R １１１６ , L １１１１ and L １１１２ At least two of them may be joined together to form a ring, n １１１１ and n １１１２ Each of these is an integer between 0 and 5, independently of the others.

[0204] [R １１１１ ~R １１１６ ] R １１１１ ~R １１１６ Each of these independently represents a hydrogen atom or a group selected from the hydrocarbon group A, which may have substituents. The group selected from the hydrocarbon group A, which may have substituents, is synonymous with the description given in the explanation of the terms above. From the standpoint of the stability of the compound, R １１１１ and R １１１２ A hydrogen atom is preferred, R １１１３ ~R １１１６ Preferably, the group consists of a hydrogen atom and an alkyl group as described in the explanation of the terms above, more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, and an ethyl group.

[0205] [L １１１１ , L １１１２ ] L １１１１ and L １１１２Each of these independently represents a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents. A group selected from hydrocarbon group A which may have substituents, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents is synonymous with the description given in the explanation of the terms above. From the standpoint of the stability of the compound, L １１１１ and L １１１２ Preferably, R is a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, an oxygen atom, or a carbonyl group. １１１３ ~R １１１６ , L １１１１ and L １１１２ At least two of them may be joined together to form a ring.

[0206] [Y １１１１ , Y １１１２ ] Y １１１１ and Y １１１２ Each of these independently represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, a hydroxyl group which may have substituents, or a silyl group which may have substituents. A group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, a hydroxyl group which may have substituents, or a silyl group which may have substituents is synonymous with the description given in the explanation of the terms above. From the standpoint of the stability of the compound, Y １１１１ and Y １１１２ The hydrogen atom is preferably a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, or an aromatic group which may have substituents; more preferably a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, and a hydrogen atom is particularly preferred.

[0207] [n １１１１ , n １１１２ ] n １１１１ and n １１１２Each of these is an integer from 0 to 5, independently of the others. From the standpoint of the stability of the compound, n １１１１ and n １１１２ The integer is preferably between 0 and 2.

[0208] [Substituents] These R １１１１ ~R １１１６ , L １１１１ , L １１１２ , Y １１１１ and Y １１１２ Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group described in the above-mentioned explanations, and are preferably groups selected from the substituent group W1.

[0209] <Preferred form of formula (1-1)> The polymer compound according to this embodiment includes a repeating unit represented by formula (1-1), wherein R in formula (1-1) １１１ is a methyl group, R １１２ ~R １１３ Preferably, it is a hydrogen atom.

[0210] <Example Structure of Repeating Unit Represented by Formula (1-1)> Specific examples of repeating units represented by formula (1-1) are shown below. The present invention is not limited to these examples.

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218] <Preferred form of formula (1-2)> The polymer compound according to this embodiment includes a repeating unit represented by formula (1-2), wherein R in formula (1-2) １２１ and R １２２ However, from the standpoint of compound stability, it is preferable that each component be either a hydrogen atom or a methyl group, independently of the others.

[0219] <Example Structure of Repeating Unit Represented by Formula (1-2)> Specific examples of repeating units represented by formula (1-2) are shown below. The present invention is not limited to these examples.

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227] <Preferred form of formula (1-3)> The polymer compound according to this embodiment includes a repeating unit represented by formula (1-3), wherein R in formula (1-3) １３１ ~R １３３ Preferably, it is a hydrogen atom.

[0228] <Example Structure of Repeating Unit Represented by Formula (1-3)> Specific examples of repeating units represented by formula (1-3) are shown below. The present invention is not limited to these examples.

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236] <Example Structures of Compounds Represented by Formula (2)> Examples of compounds represented by Formula (2) include, but are not limited to, those represented by Formula (2)-1 to Formula (2)-210. Furthermore, these compounds may have substituents.

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260] <Example Structures of the Group Represented by Formula (3)> Examples of the group represented by formula (3) include, but are not limited to, the groups represented by formulas (3)-1 to (3)-31. Furthermore, these groups may have substituents.

[0261]

[0262]

[0263] <Optional Repeating Units> The polymer compound in this embodiment may contain repeating units (R) other than at least one selected from the group consisting of repeating units represented by formula (1-1), repeating units represented by formula (1-2), and repeating units represented by formula (1-3). Here, the repeating units (R) do not include the repeating units represented by formula (1-1), repeating units represented by formula (1-2), and repeating units represented by formula (1-3), but for example, the repeating units represented by formulas (8), (9), and (11) above. By including repeating units other than those represented by formula (1-1), repeating units represented by formula (1-2), and repeating units represented by formula (1-3), the durability of the polymer compound is improved.

[0264] The repeating unit (R) is not particularly limited, but 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, polycarbonate, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyester, polyolefin, polyphenylene sulfide, aromatic polyamine, polyamine, polyurea, silicone resin, epoxy resin, polyvinyl chloride, and repeating units constituting fluoropolymers.

[0265] In particular, repeating units comprising at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, polycarbonate, polyalkyl-substituted maleimide, and polyaryl-substituted maleimide are more preferred because they generally have excellent optical properties. From the viewpoint of compound stability, repeating units comprising polystyrene, polymethacrylic acid ester, polyalkyl-substituted maleimide, or polyaryl-substituted maleimide are most preferred. Preferred examples of polymethacrylic acid esters include polyadamantyl methacrylate (poly AdMA), polyalkyloxycarbonylaminoethyl methacrylate, polymethyl methacrylate (PMMA), and poly(cyclic or linear) alkyl methacrylate. Preferred examples of polyalkyl-substituted maleimide include polymethyl maleimide, polyethyl maleimide, and polypropyl maleimide. Preferred examples of polyaryl-substituted maleimide include polyphenyl maleimide, polytolyl maleimide, and polynaphthyl maleimide.

[0266] The following are specific examples of repeating units (R) in this embodiment. The present invention is not limited to these examples.

[0267]

[0268]

[0269]

[0270]

[0271] <Examples of Preferred Polymer Compounds> The following are preferred specific examples of polymer compounds in this embodiment. The present invention is not limited to these. PA represents a repeating unit represented by formula (1-1), a repeating unit represented by formula (1-2), or a repeating unit represented by formula (1-3), and PB and PC represent repeating units (R). The asterisk (*) in the PA column of the table represents a number from 1 to 3.

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282] <Substituted Carboxylic Acid Repeating Units> The polymer compound according to this embodiment may have at least one repeating unit selected from the group consisting of repeating units represented by formula (1-1), repeating units represented by formula (1-2), and repeating units represented by formula (1-3), as well as a substituted carboxylic acid repeating unit (C-1) which is different from repeating unit (R). The usefulness of the substituted carboxylic acid repeating unit (C-1) is that by modifying the carboxylic acid residue after dye introduction, durability, solubility, and / or substrate adhesion can be improved. Groups that can be modified on carboxylic acid residues include the hydrocarbon group A described in the explanation of the terms above, and the aromatic group described in the explanation of the terms above. From the viewpoint of compound stability, hydrocarbon group A is preferred, more preferably hydrocarbon group A having 1 to 10 carbon atoms, and particularly preferably hydrocarbon group A having 1 to 6 carbon atoms.

[0283] In cases where the polymer compound according to this embodiment contains repeating units represented by formula (1-3), it may also have a substituted carboxylic acid repeating unit (C-1) represented by the following formula (C-1) as a repeating unit different from the repeating unit (R) represented by formula (1-3). The useful feature of the substituted carboxylic acid repeating unit (C-1) is that by modifying the carboxylic acid residue after dye introduction, durability, solubility, and / or substrate adhesion can be improved.

[0284]

[0285] [In formula (C-1), R Ｃ１１ ~R Ｃ１３ Each independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom, R Ｃ１４ Each of these is independently a group selected from hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, n Ｃ１２ If the number is 2 or more, the R Ｃ１４ is another R Ｃ１４ It may also be bonded to form a ring, R Ｃ１５Each of these is independently a single bond, a optionally substituted divalent alkyl group, an optionally substituted divalent aromatic group, or an optionally substituted divalent aralkyl group, Y Ｃ１１ Each of these is independently a hydrogen atom, a group selected from hydrocarbon group A, or an aromatic group which may have substituents, n Ｃ１１ n is an integer between 1 and 5. Ｃ１２ n is an integer between 0 and 4, where n Ｃ１１ to n Ｃ１２ The sum of the numbers is 5 or less.

[0286] [R Ｃ１１ ~R Ｃ１５ ] R Ｃ１１ ~R Ｃ１５ R in equation (1-3) １３１ ~R １３５ It is synonymous with [the above].

[0287] [n Ｃ１１ , n Ｃ１２ ] n Ｃ１１ , n Ｃ１２ n in equation (1-3) １３１ , n １３２ It is synonymous with [the above].

[0288] [Y Ｃ１１ ] Y Ｃ１１ These are, independently, a hydrogen atom, a hydrocarbon group A as described in the explanation of the terms above, and an aromatic group as described in the explanation of the terms above. From the viewpoint of the stability of the compound, hydrocarbon group A is preferred, more preferably a hydrocarbon group A having 1 to 10 carbon atoms, and particularly preferably a hydrocarbon group A having 1 to 6 carbon atoms. Also, Y Ｃ１１ If the atom is a hydrogen atom, it is thought that it may be possible to improve heat resistance by utilizing hydrogen bonding.

[0289] <Crosslinking Group> The polymer compound according to this embodiment may have a crosslinking group. Having a crosslinking group allows for crosslinking after poling treatment, improving the durability of the compound. Examples of crosslinking groups include vinyl group, acryloyl group, methacryloyl group, allyl group, thiol group, polyamine, polyol, isocyanate group, cyanoacryloyl group, cinnamyl group, cinnamoyl group, cinnamyridene group, cinnamyridene acetyl group, α-methylcinnamyridene group, α-methylcinnamyridene acetyl group, α,γ-dimethylcinnamyridene group, α,γ-dimethylcinnamyridene acetyl group, α-phenylcinnamyridene group, α-phenylcinnamyridene acetyl group, α-phenoxycinnamyridene group, α-phenoxycinnamyridene acetyl group, α-cyanocinnamyridene group, α-cyanocinnamyridene acetyl group, chalcone residue, oxetane group, epoxy group, isocoumarin residue, 2,5-dimethoxystilbene residue, thymine residue, stilpyridinium residue, maleimide residue, α-phenylmaleimide residue, anthracene residue, 2-pyridinium Examples include ron residues, vinyl ether groups, trifluorovinyl ether groups, benzocyclobutene groups, 1-phenyloxybenzocyclobutene groups, and their derivatives. Preferably, examples include acryloyl groups, methacryloyl groups, thiol groups, isocyanate groups, blocked isocyanate groups, cinnamoyl groups, cinnamyridene groups, α-cyanocinnamyridene groups, anthracene residues, maleimide residues, benzocyclobutene groups, and 1-phenyloxybenzocyclobutene groups. More preferably, examples include acryloyl groups, thiol groups, isocyanate groups, blocked isocyanate groups, anthracene residues, maleimide residues, benzocyclobutene groups, and 1-phenyloxybenzocyclobutene groups. Particularly preferred are acryloyl groups, isocyanate groups, blocked isocyanate groups, anthracene residues, maleimide residues, and 1-phenyloxybenzocyclobutene groups.

[0290] The polymer compound according to this embodiment may have repeating units containing crosslinking groups. Having repeating units containing crosslinking groups allows for crosslinking after poling treatment, improving the durability of the compound. Examples of crosslinking groups include the crosslinking groups described above, and preferred crosslinking groups are also as described above.

[0291] <Examples of repeating units containing crosslinking groups> The following are preferred specific examples of repeating units (CL) containing crosslinking groups. The present invention is not limited to these.

[0292]

[0293] <Examples of Polymer Compounds> The following are preferred specific examples of polymer compounds in this embodiment. The present invention is not limited to these. PA represents a repeating unit represented by formula (1-1), a repeating unit represented by formula (1-2), or a repeating unit represented by formula (1-3), and PCL represents a repeating unit (CL). The asterisk (*) in the PA column of the table represents a number from 1 to 3.

[0294]

[0295] When expressing the content of groups derived from the nonlinear optically active compound in the polymer compound according to this embodiment as a mole percentage, there are no particular restrictions on the mole percentage of groups derived from the nonlinear optical compound relative to the total of each repeating unit of the polymer compound according to this embodiment. However, from the viewpoint of balancing electro-optical effect and solubility, the lower limit is preferably 0.1 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more. The upper limit is preferably 80 mol% or less, more preferably 60 mol% or less, even more preferably 40 mol% or less, and particularly preferably 20 mol% or less.

[0296] When expressing the content of at least one repeating unit selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3) in the polymer compound according to this embodiment as a mole percentage, there are no particular restrictions on the total mole percentage of the repeating units represented by formulas (1-1) to (1-3) relative to the total of each repeating unit of the polymer compound according to this embodiment. However, from the viewpoint of balancing electro-optic effect and solubility, the lower limit is preferably 0.1 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more. The upper limit is preferably 80 mol% or less, more preferably 60 mol% or less, even more preferably 40 mol% or less, and particularly preferably 20 mol% or less.

[0297] When expressing the content of groups derived from the nonlinear optically active compound in the polymer compound according to this embodiment as a mass ratio, there are no particular restrictions on the content of groups derived from the nonlinear optically active compound in the polymer compound according to this embodiment. However, from the viewpoint of balancing electro-optical effect and solubility, the content of groups derived from the nonlinear optically active compound in the polymer compound according to this embodiment is preferably 1% by mass or more as a lower limit, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 80% by mass or less as an upper limit, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0298] The weight-average molecular weight of the polymer compound according to this embodiment is not particularly limited, but is preferably 0.5 million or more, more preferably 10,000 or more, and even more preferably 30,000 or more, as this improves durability. Furthermore, for solubility, it is preferably 500,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less, and particularly preferably 100,000 or less. The weight-average molecular weight of the polymer compound according to this embodiment is confirmed by measuring the weight-average molecular weight of polystyrene as a standard using GPC.

[0299] There are no particular restrictions on the molecular weight distribution of the polymer compound according to this embodiment, but it is preferably 5 or less, more preferably 3 or less, and even more preferably 2.5 or less. From the viewpoint of performance improvement, it is preferable that the molecular weight distribution of the polymer compound according to this embodiment is 3 or less. The molecular weight distribution of the polymer compound according to this embodiment is confirmed by measuring the ratio of the number average molecular weight to the weight average molecular weight when polystyrene is used as a standard by GPC.

[0300] There are no particular limitations on the glass transition temperature (Tg) of the polymer compound according to this embodiment, but it is generally between 40°C and 300°C. A temperature of 45°C or higher is preferred, 50°C or higher is more preferred, and 80°C or higher is even more preferred, as this improves heat resistance. Furthermore, from the viewpoint of the polling process, a temperature of 280°C or lower is preferred, 230°C or lower is more preferred, 200°C or lower is even more preferred, and 180°C or lower is even more preferred. The Tg of the polymer compound according to this embodiment is confirmed by measuring the temperature corresponding to the intersection of the gradient of the endothermic rising portion of the baseline shift of the DSC curve associated with the glass transition and the baseline using a differential scanning calorimeter (DSC).

[0301] There are no particular restrictions on the decomposition temperature (Td) of the polymer compound according to this embodiment, but it is preferably 0°C or higher, more preferably 40°C or higher, and even more preferably 80°C or higher. The Td of the polymer compound according to this embodiment can be confirmed by measuring the temperature at which the mass decreases by 5% using a thermogravimetric differential thermal analyzer (TG-DTA).

[0302] <Composition> The composition according to the embodiment of the present invention comprises at least a polymer compound according to the embodiment of the present invention and an organic solvent. The composition may also contain polymer materials, nonlinear optically active compounds, and other components.

[0303] Examples of combinations of nonlinear optically active materials and solvents contained in the composition include: • A nonlinear optically active polymer compound / solvent containing at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3) • A nonlinear optically active compound / solvent containing at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3) • A nonlinear optically active polymer compound / solvent containing at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula ( Nonlinear optically active polymer compounds / polymer materials / solvents containing at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3) / Nonlinear optically active polymer compounds / solvents not having any of the repeating units represented by formula (1-1), formula (1-2), and formula (1-3) / Nonlinear optically active polymer compounds / solvents Compound / A nonlinear optically active polymer compound containing at least one selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3) / A nonlinear optically active polymer compound that does not have any of the repeating units represented by formula (1-1), formula (1-2), and formula (1-3) / A solvent selected from the group consisting of repeating units represented by formula (1-1), formula (1-2), and formula (1-3) A nonlinear optically active polymer compound containing at least one of the repeating units represented by formula (1-1), formula (1-2), and formula (1-3) / polymer material / solvent.Nonlinear optically active polymer compounds, polymer materials, and solvents that do not have either the repeating unit represented by formula (1-2) or the repeating unit represented by formula (1-3) may each be included in the composition in quantities of one or more.

[0304] [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 solvents that can be used in the composition are not particularly limited as long as they can dissolve the polymer compound containing at least one selected from the group consisting of the repeating unit represented by formula (1-1), the repeating unit represented by formula (1-2), and the repeating unit represented by formula (1-3). Examples include 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, 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, 3-methoxybutyl acetate, and isopropyl acetate. Esters such as pyryl, butyl acetate, isobutyl acetate, ethyl lactate, γ-butyrolactone, ethyl benzoate, methyl benzoate, benzoyl benzoate, 2-ethylhexyl benzoate, 4-methylbenzoate ethyl; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone; methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, isobutyl alcohol, tert-butyl Alcohols such as pentanol, 2-methylbutanol, 2-methyl-2-butanol, cyclohexanol, 2-methylpentanol, octanol, 2-ethylhexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc.; Glycols such as ethylene glycol, propylene glycol, hexylene glycol, trimethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, etc.Examples 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, anisole, etc. These organic solvents may be used individually or in combination of two or more.

[0305] Of the above organic solvents, chlorobenzene, orthodichlorobenzene, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxybenzotrifluoride, 3-methoxybenzotrifluoride, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are more preferred from the viewpoint of applicability, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are even more preferred, and cyclopentanone, cyclohexanone, toluene, anisole, and dibromomethane are particularly preferred.

[0306] [Polymer material] From the viewpoint of improving the heat resistance of the composition, it is preferable that the composition according to the embodiment of the present invention includes a polymer material. As for the polymer material, there are no particular restrictions as long as it is a polymer compound that can disperse a nonlinear optical material, but a transparent polymer that does not scatter is preferred for use as an optical material. Examples include (meth)acrylate polymers (e.g., polymethyl methacrylate (PMMA)), polyamides, polyimides, polycarbonates, polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly AdMA), 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, and copolymers thereof. Of these, at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, and polymers thereof is preferred from the viewpoint of molecular orientation. Furthermore, methyl poly(meth)acrylate is preferred as the poly(meth)acrylic acid ester. The above organic polymers may be used individually or in combination of multiple types. In this specification, the polymer material can also be said to be a polymer compound that does not have nonlinear optical activity.

[0307] [Other Components] The compositions according to the embodiments of the present invention may contain other components not listed above. There are no particular limitations on the components that the composition may further contain, as long as they do not hinder the purpose for which the composition is used. However, as long as the effects of the present invention are not impaired, the composition may optionally contain antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesion aids such as silane coupling agents, polymer matrix crosslinking agents, compatibilizers, curing agents, pigments, preservative stabilizers, defoaming agents, and the like.

[0308] [Content] There are no particular restrictions on the content of each component in the composition according to the embodiment of the present invention. There are no particular restrictions on the content of the nonlinear optically active polymer compound in the composition, but it is preferable to have a higher content of the component exhibiting nonlinear optical activity. For example, it is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, and even more preferably 10 to 100% by mass, based on the total mass of solids contained in the composition.

[0309] There are no particular restrictions on the content of organic solvents in the composition, but from the viewpoint of film uniformity, it is preferably 60 to 99% by mass of the total mass of the composition, more preferably 70 to 99% by mass, and even more preferably 80 to 98% by mass, from the viewpoint of ensuring the stability of the composition.

[0310] <Nonlinear Optical Element> An embodiment of the present invention comprises a film containing the above-mentioned polymer compound.

[0311] The nonlinear optical element is not particularly limited as long as it uses the above-mentioned composition or a nonlinear optically active polymer compound and operates based on a nonlinear optical effect, but examples include wavelength conversion elements, photorefractive elements, and electro-optic elements. Of these, nonlinear optical elements that operate based on an electro-optic effect are preferred, and more specifically, electro-optic elements such as optical switches, optical modulators, and phase shifters are preferred. In one embodiment, an optical modulator equipped with the above-mentioned nonlinear optical element can be used.

[0312] As an electro-optic element, it is preferable to use an element having a structure in which a film formed from the above-mentioned composition or a nonlinear optically active polymer compound is formed on a substrate and sandwiched between electrode pairs for input electrical signals.

[0313] There are no particular restrictions on the film thickness of the film formed from the above-mentioned composition or nonlinear optically active polymer compound, but to effectively utilize the nonlinear effect, it is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 0.8 μm or more. Furthermore, to avoid obstructing the guidance of light, it is preferably 50 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

[0314] Materials that can be used to construct such a substrate include, for example, 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, polyetherketone, and polyimide.

[0315] 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, poly(p-phenylenevinylene), and polyacetylene. The conductive film is formed using known dry deposition methods such as vapor deposition and sputtering, or known wet deposition methods such as immersion coating and electrolytic deposition, and a pattern may be formed 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" in this specification) during poling and operation as an element.

[0316] The substrate surface may further have an adhesive layer to improve the adhesion between the film formed thereon and the substrate, a leveling layer to smooth out surface irregularities, or some intermediate layer that provides these functions together, as needed. There are no particular restrictions on the material used to form such a film, but known materials such as acrylic resins, methacrylic resins, amide resins, vinyl chloride resins, vinyl acetate resins, phenolic resins, urethane resins, vinyl alcohol resins, acetal resins, etc. and copolymers thereof; crosslinked materials such as zirconium chelate compounds, titanium chelate compounds, silane coupling agents, etc., and co-crosslinked materials thereof can be used.

[0317] The electro-optic element is preferably formed to include a waveguide structure, and it is particularly preferable to incorporate a film or nonlinear optically active polymer compound formed from the above-mentioned composition into the core layer of the waveguide.

[0318] A cladding layer (hereinafter also referred to as the "lower cladding layer" in this specification) may be formed between the core layer containing a film or nonlinear optically active polymer compound formed from the above-described composition and the substrate. This lower cladding layer can be any material that 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 cladding layer include, for example, UV-curable or thermosetting resins such as acrylic, epoxy, oxetane, thiirane, and silicone resins; polyimide; and glass.

[0319] After forming a core layer with the above-described composition or nonlinear optically active polymer compound, a cladding layer (hereinafter also referred to as the "upper cladding layer" in this specification) may be formed on top of it in the same manner as the lower cladding layer. This forms a slab-type waveguide with the configuration of substrate / lower cladding layer / core layer / upper cladding layer.

[0320] After forming the core layer, the core layer can be patterned using known methods employing semiconductor process technologies such as reactive ion etching (RIE), photolithography, and electron beam lithography to form channel-type waveguides or ridge-type waveguides. Alternatively, a channel-type waveguide can be formed by patterning and irradiating a portion of the core layer with UV light, an electron beam, or the like, thereby changing the refractive index of the irradiated area.

[0321] A basic electro-optic element can be formed by forming electrodes (hereinafter also referred to as "upper electrodes" in this specification) for applying an input electrical signal on the surface of the upper cladding layer in a desired region of the upper cladding layer.

[0322] When forming channel-type waveguides or ridge-type waveguides as described above, known device structures such as linear, Y-branch, directional coupler, and Mach-Zehender types can be configured as the core layer pattern, and these can be applied to known optical information communication devices such as optical switches, optical modulators, and phase shifters. One example of application to optical information communication devices is the application to an optical modulator equipped with a nonlinear optical element that operates based on the electro-optic effect described above.

[0323] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and can be modified and implemented as such without departing from its essence.

[0324] <Synthesis of EO Polymers> EO polymers 1 to 17 were synthesized using the following method.

[0325] <Synthesis of Compound 1> Compound 1, described below, was synthesized in the same manner as compound 10b described in Journal of Polymer Science Part A: Polymer Chemistry, 2010, 49, 47-54.

[0326]

[0327] <Synthesis of Compound 2>

[0328]

[0329] In a 100 mL flask, a solution of compound 1 (1.00 g, 1.97 mmol) in THF (10 mL) was stirred at 25°C, and 1 M tetrabutylammonium fluoride (TBAF)-THF solution (2.2 mL) was added dropwise. After addition, the mixture was stirred at 25°C for 3 hours. After the reaction was complete, 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 compound 2 (722 mg, yield 88.8%).

[0330] The results of the NMR measurement of compound 2 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)

[0331] <Synthesis of Nonlinear Optically Active Compound 1>

[0332]

[0333] In a 100 mL three-necked flask, under a nitrogen stream, a solution of compound 2 (0.5 g, 1.27 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (521 mg, 1.65 mmol) in THF (5 mL) was added, to which ethanol (10 mL) was added and the mixture was stirred at 25 °C for 16 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 1 (581 mg, yield 66.2%).

[0334] The results of the NMR measurement of nonlinear optically active compound 1 are shown below. １ H-NMR (400MHz, CDCl ３) δ7.78 (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)

[0335] <Synthesis of Monomer 1>

[0336]

[0337] Under a nitrogen atmosphere, 10.0 g, 43.4 mmol of 1-[2-(methacryloyloxy)ethyl succinate], 5.5 g, 11.0 mmol of N-hydroxysuccinimide, and 531 mg, 1 mmol of 4-dimethylaminopyridine (DMAP) were dissolved in 100 mL of THF. After cooling to 0°C, a solution of N,N'-dicyclohexylcarbodiimide (DCC) (9.86 g, 11.0 mmol) in 20 mL of THF was added. After addition, the mixture was stirred at room temperature for 3 hours. Subsequently, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain monomer 1 (12.0 g, yield 79.8%).

[0338] <Synthesis of Base Polymer 1>

[0339]

[0340] 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 the temperature was raised to 70°C and stirred for a further 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 filtered. The filtered solid was rinsed with hexane (120 mL). The filtered material was redissolved in tetrahydrofuran (28 mL) and added dropwise to methanol (280 mL). The resulting solid was filtered. The filtered material was redissolved in THF (28 mL) and added dropwise to hexane (280 mL). The resulting solid was filtered and vacuum-dried at 50°C for 5 hours to obtain base polymer 1 (5.52 g, yield 39.1%).

[0341] The molecular weight of the obtained base polymer 1 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn 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.

[0342] <Synthesis of EO Polymer 1'>

[0343]

[0344] Under a nitrogen atmosphere, base polymer 1 (3.0 g) and compound 2 (285 mg, 0.77 mmol) were dissolved in deoxygenated THF (62 mL), and 4-dimethylaminopyridine (DMAP) (5.68 g, 46.3 mmol) was added. The mixture was then stirred in an oil bath at 50°C for 2 hours. Subsequently, dehydrated methanol (2.0 mL) was added, and the mixture was stirred in an oil bath at 50°C for 4 hours. After cooling to room temperature, the reaction solution was added dropwise to methanol (200 mL), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (150 mL), and vacuum-dried under heating at 50°C to obtain EO polymer 1' (2.34 g).

[0345] <Synthesis of EO Polymer 1>

[0346]

[0347] Under a nitrogen atmosphere, EO polymer 1' (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), then anhydrous ethanol (40 mL) was added, and the mixture was stirred at 50°C for 8 hours. After cooling to room temperature, the reaction solution was added dropwise to methanol (440 mL). The resulting solid was filtered and rinsed with methanol (220 mL) to obtain a green solid. The green solid was redissolved in dichloromethane (80 mL), 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 filter was rinsed with hexane (200 mL) to obtain EO polymer 1 (1.96 g). The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) DSC-60APlus manufactured by Shimadzu Corporation. Tg was defined as the temperature corresponding to the intersection of the baseline and the slope of the rise portion of the endothermic process in the baseline shift of the DSC curve showing the change in heat quantity when the temperature was increased at 10°C / min. Based on this measurement, the Tg of EO polymer 1 was found to be 105°C.

[0348] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 contained in EO polymer 1 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 was 13% by mass (5 mol%).

[0349] <Synthesis of Base Polymer 2>

[0350]

[0351] Styrene (978 mg, 9.40 mmol), N-ethylmaleimide (705 mg, 5.64 mmol), and N-succinimidyl 3-maleimidopropionic acid (1.0 g, 3.76 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated N,N-dimethylformamide (4.0 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (19 mg, 0.07 mmol) was added. Further deoxygenated N,N-dimethylformamide (4.0 mL) was added, purged with nitrogen, and the reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was cooled to 0°C and diluted with tetrahydrofuran (200 mL). The diluted solution was added dropwise to methanol (400 mL), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (200 mL) and vacuum-dried. 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 filtered. The filtered solid was rinsed with methanol (200 mL) and vacuum-dried to obtain base polymer 2 (1.72 g, yield 63.2%).

[0352] The molecular weight of the obtained base polymer 2 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn 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.

[0353] <Synthesis of EO Polymer 2'>

[0354]

[0355] Under a nitrogen atmosphere, base polymer 2 (1.45 g) and compound 2 (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 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 filtered and rinsed with methanol (100 mL). The filtered material was dissolved in dichloromethane (10 mL) and added dropwise to methanol (300 mL). The resulting solid was filtered and rinsed with methanol (100 mL). The filtered material was redissolved in dichloromethane (10 mL) and added dropwise to hexane (200 mL). The resulting solid was filtered, rinsed with hexane (100 mL), and then vacuum-dried to obtain EO polymer 2' (587 mg, yield 37.9%). The content of the group obtained by removing one hydrogen atom from compound 2 in EO polymer 2' was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content of the group obtained by removing one hydrogen atom from compound 2 was found to be 16% by mass (6 mol%).

[0356] <Synthesis of EO Polymer 2>

[0357]

[0358] Under a nitrogen atmosphere, EO polymer 2' (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), then anhydrous ethanol (10.6 mL) was added, and the mixture was stirred at 50°C for 15 hours. After 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 filtered 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, after which the clay was removed by filtration. Activated clay (700 mg) was added to the filtrate, and the mixture was stirred at room temperature for 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 filtered and rinsed with methanol (70 mL) to obtain EO polymer 2 (432 mg).

[0359] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 in EO polymer 2 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 was 25% by mass (6 mol%). <Synthesis of base polymer 3>

[0360]

[0361] 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, purged with nitrogen, dissolved in deoxygenated N,N-dimethylformamide (4.0 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (20 mg, 0.07 mmol) was added. Further deoxygenated N,N-dimethylformamide (4.0 mL) was added, purged with nitrogen, and the reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was cooled to 0°C and diluted with tetrahydrofuran (38 mL). The diluted solution was added dropwise to methanol (380 mL), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (200 mL) and vacuum-dried. 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 filtered. The filtered solid was rinsed with methanol (200 mL) and vacuum-dried to obtain base polymer 3 (2.38 g, yield 61.8%).

[0362] The molecular weight of the obtained base polymer 3 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn 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.

[0363] <Synthesis of EO Polymer 3'>

[0364]

[0365] Under a nitrogen atmosphere, base polymer 3 (1.02 g) and compound 2 (285 mg, 0.72 mmol) were dissolved in anhydrous chloroform (30.4 mL), and 4-dimethylaminopyridine (DMAP) (884 mg, 7.2 mmol) was added. The mixture was then 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 cooling to room temperature, the reaction solution was added dropwise to methanol (300 mL), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (100 mL), and vacuum-dried under heating at 60°C to obtain EO polymer 3'.

[0366] The content of the group obtained by removing one hydrogen atom from compound 2 in EO polymer 3' was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content of the group obtained by removing one hydrogen atom from compound 2 was found to be 7.6 mass% (2.5 mol%).

[0367] <Synthesis of EO Polymer 3>

[0368]

[0369] Under a nitrogen atmosphere, EO polymer 3' (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), then anhydrous ethanol (25 mL) was added, and the mixture was stirred at 60°C for 12 hours. After 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 filtered and rinsed with methanol (100 mL) to obtain a green solid.

[0370] Under a nitrogen atmosphere, the obtained 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), then anhydrous ethanol (5 mL) was added, and the mixture was stirred at 60°C for 6 hours. After 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 filtered 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 stirred at room temperature for another 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 filtered 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 filtered and rinsed with hexane (100 mL) to obtain EO polymer 3 (80 mg).

[0371] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 in EO polymer 3 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 was 9.1% by mass (2.5 mol%). <Synthesis of base polymer 4>

[0372]

[0373] Methyl methacrylate (MMA) (100.0 g, 1.00 mol) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (62.7 g, 0.25 mol) were dissolved in deoxygenated toluene (375 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (620 mg, 25 mmol) were added. After purging with nitrogen, the reaction solution was heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (2.5 L), and the resulting solid was filtered. The filtered solid was dissolved in tetrahydrofuran (1.25 L) and filtered. The filtrate was concentrated to 700 mL using an evaporator, and then added dropwise to methanol (6.7 L), and stirred at room temperature for 30 minutes. The solid was then filtered off, and the filtered material was rinsed with methanol (2.2 L) and vacuum-dried at 60°C for 8 hours to obtain base polymer 4 (110 g).

[0374] The molecular weight of the obtained base polymer 4 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: THF, column temperature: 40°C). The weight-average molecular weight Mw was 70,600, and the number-average molecular weight Mn was 38,900.

[0375] <Synthesis of EO Polymer 4>

[0376]

[0377] Under a nitrogen atmosphere, base polymer 4 (30.0 g, 0.22 mol) and nonlinear optically active compound 1 (7.58 g, 11 mmol) were dissolved in deoxygenated 1,4-dioxane (450 mL) and stirred at room temperature for 5 minutes. Then, dibutyltin dilaurate (DBTDL) (6.6 mL) was added and the mixture was stirred in an oil bath at 100°C for 2 hours. Subsequently, dehydrated methanol (35.5 mL) was added and the mixture was stirred in an oil bath at 100°C for 1 hour. 24 mL of the reaction solution was withdrawn and added dropwise to hexane (240 mL), and the resulting solid was filtered off. The filtered solid was rinsed with hexane (240 mL) to obtain EO polymer 4 (1.33 g).

[0378] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 contained in EO polymer 4 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 was 23 mass% (5 mol%).

[0379] <Synthesis of base polymer 5>

[0380]

[0381] 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 the temperature was raised to 70°C and stirred for a further 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 filtered off. The filtered solid was rinsed with hexane (120 mL) and vacuum dried to obtain base polymer 5 (3.76 g, yield 50.6%).

[0382] The molecular weight of the obtained base polymer 5 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn 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.

[0383] <Synthesis of EO Polymer 5>

[0384]

[0385] Under a nitrogen atmosphere, base polymer 5 (439 mg) and nonlinear optically active compound 1 (100 mg) were dissolved in dehydrated 1,4-dioxane (0.57 mL), and dibutyltin dilaurate (DBTDL) (44 μL) was added. The mixture was stirred in an oil bath at 110°C for 3 hours. Subsequently, dehydrated methanol (0.57 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 filtered off. The filtered solid was purified by activated clay treatment (solvent: DCM) and reprecipitation (rich solvent: DCM, poor solvent: methanol) to obtain EO polymer 5 (425 mg).

[0386] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 in EO polymer 5 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 was 17% by mass (5 mol%).

[0387] <Synthesis of Compound 3> Compound 3, described below, was synthesized in the same manner as Compound 23 described in International Publication No. 2025 / 205646.

[0388]

[0389] <Synthesis of Compound 4> Compound 4, described below, was synthesized by the same method as for the secondary dye 10 described in International Publication No. 2025 / 205646.

[0390]

[0391] <Synthesis of Nonlinear Optically Active Compound 2> The following nonlinear optically active compound 2 was synthesized by the same method as dye 10 described in International Publication No. 2025 / 205646.

[0392]

[0393] <Synthesis of Compound 5>

[0394]

[0395] In a 10 L three-necked flask, under a nitrogen stream, a solution of 2-hydroxymethyl acetate (200 g, 2.22 mol), triethylamine (TEA) (371 mL, 2.66 mol), and 4-dimethylaminopyridine (DMAP) (2.72 g, 22.3 mmol) in dichloromethane (100 mL) was cooled to -10°C, and while stirring, a solution of methacryloyl chloride (255.3 g, 2.44 mol) in dichloromethane (840 mL) was slowly added. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred for 5.5 hours. Then, the reaction solution was cooled again to -10°C, and deionized water (2 L) was added. The organic layer was dried over sodium sulfate, filtered, and then concentrated under reduced pressure using an evaporator to obtain compound 5 (400 g, yield 87.9%).

[0396] <Synthesis of Compound 6>

[0397]

[0398] In a 20 L three-necked flask, under a nitrogen stream, a solution of compound 5 (400 g, 2.02 mol) in tetrahydrofuran (2.46 L) was cooled to -10°C, and 0.4 M sodium hydroxide aqueous solution (5.05 L) was slowly added while stirring. After the addition was complete, the mixture was stirred at -10°C to 0°C for 2.5 hours. Then, while cooling to -5°C, the reaction solution was neutralized with hydrochloric acid and extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure using an evaporator to obtain compound 6 (270.6 g, yield 77.1%).

[0399] <Synthesis of Monomer 2>

[0400]

[0401] In a 10 L three-necked flask, under a nitrogen stream, compound 6 (262.9 g, 1.82 mol) was dissolved in dichloromethane (2.63 L) to which 4-dimethylaminopyridine (DMAP) (22.3 g, 182 mmol), dibutylhydroxytoluene (440 mg, 1000 ppm), and N-hydroxysuccinimide (251.9 g, 2.18 mol) were added. The mixture was then cooled to -10°C, and 1-[2-(dimethylamino)propyl]-3-ethylcarbodiimide (EDC·HCl) (251.9 g, 2.18 mol) was slowly added while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 4 hours. Subsequently, deionized water (2 L) was added to the reaction solution, and the organic layer was recovered by liquid-liquid extraction. The recovered organic layer was dried over sodium sulfate, filtered, and then concentrated using an evaporator. Methanol (694 mL) was added to the concentrate, and the mixture was stirred at room temperature for 30 minutes. The solid was then collected by filtration and rinsed with methanol (347 mL). The resulting solid was vacuum-heat-dried at 40°C to obtain monomer 2 (143.7 g, yield 32.7%).

[0402] <Synthesis of base polymer 6>

[0403]

[0404] Methyl methacrylate (3.00 g, 30.0 mmol), N-ethyl maleimide (6.26 g, 50.0 mmol), and monomer 2 (4.82 g, 20.0 mmol) were dissolved in deoxygenated N,N-dimethylformamide (44.5 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (99.3 mg, 0.40 mmol) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C and stirred for a further 2 hours. The reaction solution was air-cooled to room temperature, and then added dropwise to tert-butyl methyl ether (445 mL), and stirred at room temperature for 20 minutes. The supernatant was removed, the residue was redissolved in tetrahydrofuran (80 mL), filtered, and then rinsed with tetrahydrofuran (29 mL). The filtrate was added dropwise to tert-butyl methyl ether (1.1 L) and stirred at room temperature for 20 minutes. The resulting solid was filtered and vacuum-dried. The obtained solid was redissolved in tetrahydrofuran (160 mL) and added dropwise to tert-butyl methyl ether (1.6 L), and stirred at room temperature for 20 minutes. The resulting solid was filtered and vacuum-dried at 50°C for 5 hours to obtain base polymer 6 (9.12 g, yield 64.8%). The molecular weight of the obtained base polymer 6 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (column: TSKgel guardcolumn SuperAW-H (6.0 mm ID × 150 mm L, 9 μm) × 2 columns, TSKgel guardcolumn SuperAW-H, developing solvent: 0.5 mass% lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight-average molecular weight Mw was 44,000 and the number-average molecular weight Mn was 13,000.

[0405] <Synthesis of EO Polymer 6'>

[0406]

[0407] Under a nitrogen atmosphere, base polymer 6 (1.41 g) and compound 4 (531 mg, 0.75 mmol) were dissolved in anhydrous chloroform (50 mL). 4-dimethylaminopyridine (DMAP) (914 mg, 7.50 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (232 mg, 1.12 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 4.5 hours. Then, anhydrous methanol (1.5 mL) was added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was filtered and rinsed with chloroform (25 mL). The filtrate was concentrated to 34.5 g using an evaporator, and the solution was added dropwise to methanol (233 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (100 mL). The filtered material was dissolved in dichloromethane (34 mL), and methanol (102 mL) was added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:3) (34 mL). The residue was redissolved in dichloromethane (34 mL), filtered, and then rinsed with dichloromethane (34 mL). The filtrate was concentrated in an evaporator to 22.5 g, and the solution was added dropwise to methanol (170 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (85 mL), and then vacuum-dried at 50°C for 5 hours to obtain EO polymer 6' (1.22 g).

[0408] <Synthesis of EO Polymer 6>

[0409]

[0410] Under a nitrogen atmosphere, EO polymer 6' (150 mg) and 2-[3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene]malononitrile (117 mg, 0.59 mmol) were dissolved in tetrahydrofuran (7.5 mL), to which ethanol (7.5 mL) was added and the mixture was stirred at 60°C for 16 hours. After cooling to room temperature, the reaction solution was concentrated in an evaporator and redissolved in dichloromethane (3 mL). The solution was added to hexane (100 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, and the filtered material was rinsed with hexane (50 mL). The filtered material was redissolved in dichloromethane (3 mL), and methanol (12 mL) was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:4) (12 mL). The residue was redissolved in dichloromethane (3 mL), added dropwise to methanol (100 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered, and the filtered material was rinsed with methanol (50 mL) and then vacuum-dried at 60°C for 6 hours to obtain EO polymer 6 (115 mg). The content of the group obtained by removing one hydrogen atom from nonlinear optically active compound 2 in EO polymer 6 was determined from the ratio of mass extinction coefficients measured using a spectrophotometer, and the content was found to be 29 mass% (7 mol%).

[0411] <Synthesis of Compound 7> Compound 7, described below, was synthesized in the same manner as 8a described in Dyes and Pigments 2021, 184, 108801.

[0412]

[0413] <Synthesis of Nonlinear Optically Active Compound 3>

[0414]

[0415] Under a nitrogen atmosphere, a solution of compound 4 (0.5 g, 0.70 mmol) and compound 7 (184 mg, 0.70 mmol) in tetrahydrofuran (25 mL) was mixed with ethanol (12.5 mL) and ammonium acetate (54.3 mg, 0.70 mmol), and the mixture was stirred at room temperature for 16 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 3 (430 mg, yield 64.1%).

[0416] The results of the NMR measurement of nonlinear optically active compound 3 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.06-7.54 (m, 16H), 6.91 (s, 2H), 6.64 (d, 1H), 6.33 (d, 1H), 4.97 (s, 2H), 3.82 (d, 4H), 3.75 (t, 2H), 3.61 (t, 2H), 2 .39 (s, 2H), 2.34 (s, 3H), 2.22 (d, 1H), 2.08 (s, 3H), 2.05 (d, 1H), 1.94 (s, 6H), 1.00 (s, 3H), 0.87 (s, 9H), 0.03 (s, 6H)

[0417] <Synthesis of base polymer 7>

[0418]

[0419] Methyl methacrylate (MMA) (22.4 g, 223.9 mmol) and monomer 2 (13.5 g, 56.0 mmol) were dissolved in deoxygenated N,N-dimethylformamide (75.6 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (278 mg, 1.12 mmol) was added. The reaction solution was then heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was cooled to 0°C, diluted with tetrahydrofuran (280 mL), and then added dropwise to methanol (3.6 L). The resulting solid was filtered off. The filtered solid was rinsed with methanol (900 mL), dissolved again in tetrahydrofuran (360 mL), and added dropwise to methanol (3.3 L). The mixture was then stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (1.5 L), and vacuum-dried to obtain base polymer 7 (28.9 g, yield 80.6%). The molecular weight of the obtained base polymer 7 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (column: TSKgel guardcolumn SuperAW-H (6.0 mm ID × 150 mm L, 9 μm) × 2, TSKgel guardcolumn SuperAW-H, developing solvent: 0.5 mass% lithium bromide / N-methyl-2-pyrrolidone solution, column temperature: 40°C). The weight-average molecular weight Mw was 50,000 and the number-average molecular weight Mn was 25,600.

[0420] <Synthesis of EO Polymer 7'>

[0421]

[0422] Under a nitrogen atmosphere, base polymer 7 (3.0 g) and compound 4 (1.51 g, 2.13 mmol) were dissolved in anhydrous chloroform (117 mL). 4-dimethylaminopyridine (DMAP) (2.60 g, 21.3 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (1.45 g, 7.03 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 4.5 hours. Anhydrous methanol (4.3 mL) was then added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was added dropwise to methanol (1.2 L). The resulting solid was filtered and rinsed with methanol (210 mL). The filtered material was dissolved in dichloromethane (30.8 mL), filtered, and then rinsed with dichloromethane (30.8 mL). The filtrate was concentrated using an evaporator until it reached 41.4 g. The concentrated solution was added dropwise to methanol (460 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (230 mL), and then vacuum-dried at 50°C for 6 hours to obtain EO polymer 7' (3.31 g).

[0423] <Synthesis of EO Polymer 7>

[0424]

[0425] Under a nitrogen atmosphere, 600 mg of EO polymer 7' and 658 mg, 2.52 mmol of compound 7 were dissolved in 30 mL of tetrahydrofuran, to which 30 mL of ethanol was added and the mixture was stirred at 60°C for 16 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator and redissolved in 12 mL of dichloromethane. The solution was added to 120 mL of hexane and stirred at room temperature for 20 minutes. The resulting solid was filtered, and the filtered material was rinsed with 60 mL of hexane. The filtered material was redissolved in 12 mL of dichloromethane, and 36 mL of methanol was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with 24 mL of a mixed solution of dichloromethane and methanol (mixing volume ratio 1:3). The residue was redissolved in 12 mL of dichloromethane, added dropwise to 120 mL of methanol, and stirred at room temperature for 20 minutes. The resulting solid was filtered, and the filtered material was rinsed with methanol (60 mL). EO polymer 7 was then vacuum-dried at 50°C for 6 hours to obtain 525 mg. The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 3 in EO polymer 7 was determined from the ratio of mass extinction coefficients measured using a spectrophotometer, and the content was found to be 39 mass% (9 mol%).

[0426] <Synthesis of base polymer 8>

[0427]

[0428] Styrene (3.13 g, 30.0 mmol), N-phenylmaleimide (3.12 g, 18.0 mmol), and N-succinimidyl 3-maleimidopropionic acid (3.20 g, 12.0 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated DMF (159 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (59.6 mg, 0.24 mmol) were added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was air-cooled to room temperature. The air-cooled reaction solution was added dropwise to methanol (1.6 L), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (0.5 L) and then tert-butyl methyl ether (0.5 L), and then vacuum-dried. The dried solid was redissolved in tetrahydrofuran (210 mL), filtered, and then rinsed with tetrahydrofuran (100 mL). The filtrate was added dropwise to methanol (3.1 L), and the resulting solid was filtered out. The filtered solid was rinsed with methanol (170 mL) and vacuum dried to obtain base polymer 8 (6.67 g, yield 70.7%). The molecular weight of the obtained base polymer 8 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: 0.5 wt% LiBr in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 78,000 and the number-average molecular weight Mn was 18,000.

[0429] <Synthesis of EO Polymer 8'>

[0430]

[0431] Under a nitrogen atmosphere, base polymer 8 (1.5 g) and compound 2 (405 mg, 1.03 mmol) were dissolved in dehydrated chloroform (47.7 mL). 4-dimethylaminopyridine (DMAP) (1.26 g, 10.3 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (319 mg, 1.55 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 14 hours. Then, dehydrated methanol (2.1 mL) was added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was filtered and rinsed with chloroform (25 mL). The solution was then concentrated using an evaporator until the volume was 34.0 g, and the concentrate was added dropwise to methanol (460 mL). The resulting solid was filtered, rinsed with methanol (150 mL), and then vacuum-dried. The obtained solid was redissolved in dichloromethane (32 mL), and hexane (96 mL) was slowly added dropwise while stirring the solution. The supernatant was removed, and the residue was washed with a mixed solvent of dichloromethane and hexane (dichloromethane:hexane = 1:3, 32 mL). The residue was dissolved in dichloromethane (16 mL), filtered, and then rinsed with dichloromethane (16 mL). The solution was concentrated using an evaporator until the volume was 21.3 g, and the concentrate was added dropwise to methanol (160 mL). The resulting solid was filtered, rinsed with methanol (80 mL), and then vacuum dried to obtain EO polymer 8' (1.42 g).

[0432] <Synthesis of EO Polymer 8>

[0433]

[0434] Under a nitrogen atmosphere, EO polymer 8' (1.34 g) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (761 mg, 2.41 mmol) were dissolved in deoxygenated tetrahydrofuran (26.8 mL), then dehydrated ethanol (26.8 mL) was added, and the mixture was stirred at 50°C for 15 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The concentrate was redissolved in dichloromethane (24.5 mL) and added dropwise to hexane (245 mL). The resulting solid was filtered and rinsed with hexane (125 mL) to obtain a green solid. After washing, the solid was redissolved in dichloromethane (40.0 mL), methanol (120 mL) was slowly added while stirring, the supernatant was removed, and the residue was washed with a mixed solvent of dichloromethane and methanol (dichloromethane:methanol = 1:3, 40 mL). The residue was redissolved in dichloromethane (40.0 mL), filtered, and then rinsed with dichloromethane (40 mL). The solution was then concentrated using an evaporator until it reached 31.9 g, and the concentrate was added dropwise to methanol (245 mL). The resulting solid was filtered, rinsed with methanol (120 mL), and then vacuum dried to obtain EO polymer 8 (1.19 g). The molecular weight of EO polymer 8 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 121,000, and the number-average molecular weight Mn was 38,000. The content of the group obtained by removing one hydrogen atom from nonlinear optically active compound 1 in EO polymer 8 was determined from the ratio of mass extinction coefficients in absorbance measurement using a spectrophotometer. The content of the group obtained by removing one hydrogen atom from nonlinear optically active compound 1 was 36 mass% (11 mol%).

[0435] <Synthesis of Compound 8>

[0436]

[0437] Under a nitrogen atmosphere, 1,5,7-triazabicyclo[4.4.0]deca-5-empolystyrene (PS-TBD) (764 mg) was added to a solution of 4,4'-difluorobenzophenone (25.0 g, 115 mmol) in acetonitrile (250 mL), and the solution was cooled to -4°C. After cooling, trimethylcyanide (TMSCN) (17.1 mL, 138 mmol) was slowly added dropwise while stirring. After addition, the mixture was stirred at room temperature for 1 hour, and then stirred at 60°C for a further 18 hours. After air cooling to room temperature, the reaction solution was filtered. Compound 8 (36.6 g, yield 96.9%) was obtained by concentrating the filtrate using an evaporator.

[0438] <Synthesis of Compound 9>

[0439]

[0440] Under a nitrogen atmosphere, a solution of compound 8 (35.5 g, 112 mmol) in tetrahydrofuran (355 mL) was cooled to -26°C, and a solution of methyllithium methoxycyclopentane (1.4 M, 96 mL, 134 mmol) was slowly added dropwise while stirring. After the addition was complete, the reaction solution was stirred at room temperature for 3 hours. The reaction solution was cooled to -22°C, hydrochloric acid (6 M, 317 mL) was slowly added dropwise, and the mixture was stirred at room temperature for 30 minutes, followed by stirring at 60°C for 2 hours. After the reaction was complete, the mixture was extracted with dichloromethane (200 mL), and the organic layer was concentrated using an evaporator. The residue was purified by silica gel column chromatography to obtain compound 9 (15.8 g, yield 53.9%).

[0441] <Synthesis of Compound 10>

[0442]

[0443] Under a nitrogen atmosphere, a pyridine (38 mL) solution of compound 9 (7.64 g, 29.1 mmol) was cooled to 0°C, and a pyridine (2.5 mL) solution of malononitrile (3.85 g, 58.2 mmol) was slowly added dropwise while stirring. After the addition was complete, the mixture was stirred at room temperature for 2 hours, then the temperature was raised to 50°C and stirred for a further 16 hours. After the reaction was complete, the mixture was air-cooled to room temperature, and the reaction solution was concentrated using an evaporator. Toluene (50 mL) was added to the concentrate, and the mixture was concentrated using an evaporator. The residue was dissolved in dichloromethane (50 mL), filtered, and then rinsed with dichloromethane (20 mL). The filtrate was slowly added dropwise to hexane (280 mL) at room temperature while stirring. The resulting solid was filtered and rinsed with a mixed solution of dichloromethane and hexane (mixing volume ratio 1:4) (20 mL). Compound 10 (7.05 g, yield 67.4%) was obtained by vacuum drying the washed solid at 50°C for 3 hours.

[0444] <Synthesis of Nonlinear Optically Active Compound 4>

[0445]

[0446] Under a nitrogen atmosphere, a solution of compound 4 (0.3 g, 0.42 mmol) and compound 10 (152 mg, 0.42 mmol) in tetrahydrofuran (15 mL) was mixed with ethanol (15 mL) and stirred at room temperature for 16 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 4 (100 mg, yield 22.5%).

[0447] The results of the NMR measurement of nonlinear optically active compound 4 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.85 (t, 1H), 7.03-7.49 (m, 18H), 6.92 (s, 2H), 6.67 (d, 1H), 6.35 (d, 1H), 4.94 (s, 2H), 3.82 (d, 4H), 3.75 (t , 2H), 3.62 (t, 2H), 2.42 (s, 2H), 2.34 (s, 3H), 2.23 (s, 2H), 1.94 (s, 6H), 0.96 (s, 6H), 0.87 (s, 9H), 0.03 (s, 6H)

[0448] <Synthesis of base polymer 9>

[0449]

[0450] Styrene (4.0 g, 38.4 mmol), N-ethylmaleimide (962 mg, 7.68 mmol), and N-succinimidyl 3-maleimidopropionate (8.18 g, 30.7 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated N,N-dimethylformamide (221.3 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (76.3 mg, 0.307 mmol) were added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was air-cooled to room temperature. The air-cooled reaction solution was added dropwise to methanol (2.2 L), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (1.1 L) and vacuum-dried. The dried solid was redissolved in tetrahydrofuran (200 mL), filtered, and then rinsed with tetrahydrofuran (90 mL). The filtrate was added dropwise to methanol (2.61 L), and the resulting solid was filtered out. The filtered solid was rinsed with methanol (1.3 L), and the base polymer 9 was obtained by vacuum drying (8.79 g, yield 66.9%). The molecular weight of the obtained base polymer 9 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 97,000 and the number-average molecular weight Mn was 35,000.

[0451] <Synthesis of EO Polymer 9'>

[0452]

[0453] Under a nitrogen atmosphere, base polymer 9 (2.4 g) and compound 4 (1.1 g, 1.55 mmol) were dissolved in anhydrous chloroform (70.2 mL). 4-dimethylaminopyridine (DMAP) (1.89 g, 15.5 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (479 mg, 2.33 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 8 hours. Then, anhydrous methanol (3.1 mL) was added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was filtered and rinsed with chloroform (50 mL). The filtrate was concentrated to 39.0 g using an evaporator, and the solution was added dropwise to methanol (2.7 L) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (1.4 L). The filtered material was dissolved in dichloromethane (42 mL), then added dropwise to methanol (420 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (420 mL), and then vacuum-dried at 50°C for 6 hours to obtain EO polymer 9' (2.53 g).

[0454] <Synthesis of EO Polymer 9>

[0455]

[0456] Under a nitrogen atmosphere, 25 mL of ethanol was added to a solution of EO polymer 9' (500 mg) and compound 10 (385 mg, 1.07 mmol) in tetrahydrofuran (25 mL), and the mixture was stirred at 60°C for 16 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The residue was redissolved in dichloromethane (5 mL), added to methanol (150 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (50 mL). The filtered material was redissolved in dichloromethane (5 mL), and methanol (15 mL) was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:3) (15 mL). The residue was redissolved in dichloromethane (5 mL), added dropwise to hexane (150 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with hexane (50 mL), and then vacuum-dried at 60°C for 6 hours to obtain EO polymer 9 (380 mg). The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 4 in EO polymer 9 was determined from the ratio of mass extinction coefficients measured using a spectrophotometer, and the content was found to be 37 mass% (9 mol%).

[0457] <Synthesis of base polymer 10>

[0458]

[0459] α-methylstyrene (1.67 g, 14.1 mmol), N-phenylmaleimide (1.46 g, 8.43 mmol), and N-succinimidyl 3-maleimidopropionic acid (1.5 g, 5.64 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated N,N-dimethylformamide (39 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (28.0 mg, 0.113 mmol) were added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was air-cooled to room temperature. The air-cooled reaction solution was added dropwise to methanol (420 mL), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (300 mL) and vacuum-dried. The dried solid was redissolved in tetrahydrofuran (45 mL), filtered, and then rinsed with tetrahydrofuran (7 mL). The filtrate was added dropwise to methanol (510 mL), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (300 mL) and vacuum dried to obtain base polymer 10 (3.71 g, yield 79.2%). The molecular weight of the obtained base polymer 10 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 40,000 and the number-average molecular weight Mn was 16,000.

[0460] <Synthesis of EO Polymer 10'>

[0461]

[0462] Under a nitrogen atmosphere, base polymer 10 (1.60 g) and compound 2 (843 mg, 2.14 mmol) were dissolved in anhydrous chloroform (48.7 mL). 4-dimethylaminopyridine (DMAP) (2.62 g, 21.4 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (663 mg, 3.21 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 8.5 hours. Anhydrous methanol (4.4 mL) was then added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was added dropwise to methanol (450 mL). After stirring at room temperature for 20 minutes, the resulting solid was filtered and rinsed with methanol (450 mL). The obtained solid was redissolved in dichloromethane (32 mL), filtered, and then rinsed with dichloromethane (32 mL). The filtrate was concentrated using an evaporator until it reached 43.5 g. The resulting solution was then added dropwise to methanol (290 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (290 mL), and then vacuum-dried at 50°C for 5 hours to obtain EO polymer 10' (2.0 g).

[0463] <Synthesis of EO Polymer 10>

[0464]

[0465] Under a nitrogen atmosphere, EO polymer 10' (1.0 g) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (590 mg, 1.87 mmol) were dissolved in deoxygenated tetrahydrofuran (50 mL), then anhydrous ethanol (50 mL) was added, and the mixture was stirred at 60°C for 18 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The resulting solid was redissolved in dichloromethane (10 mL), added dropwise to methanol (150 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (75 mL). The resulting solid was redissolved in dichloromethane (10 mL), added dropwise to methanol (150 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (75 mL). Specifically, reprecipitation was performed twice using dichloromethane and methanol. The obtained solid was redissolved in dichloromethane (10 mL), added dropwise to hexane (150 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with hexane (75 mL), and then vacuum-dried at 60°C for 6 hours to obtain EO polymer 10 (720 mg). The content of the group obtained by removing one hydrogen atom from nonlinear optically active compound 1 in EO polymer 10 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content was found to be 44 mass% (15 mol%).

[0466] <Synthesis of Monomer 3>

[0467]

[0468] Under a nitrogen atmosphere, N,N'-dicyclohexylcarbodiimide (DCC) (25.7 g, 125 mmol) was slowly added to a solution of 4-(2,5-dioxo-1H-pyrrole-1-yl)phenylacetic acid (22.5 g, 97.3 mmol) and N-hydroxysuccinimide (14.3 g, 125 mmol) in 1,2-dimethoxyethane (DME) (800 mL) and stirred at room temperature for 2.5 hours. The reaction solution was filtered, rinsed with dimethoxyethane (400 mL), and the filtrate was concentrated using an evaporator. The resulting solid was purified by silica gel column chromatography to obtain monomer 3 (23.8 g, 74.4%).

[0469] The results of the NMR measurement of monomer 3 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.45 (d, 2H), 7.37 (d, 2H), 6.86 (s, 2H), 3.98 (s, 2H), 2.84 (s, 4H), 5.83 (d, 1H), 5.30 (d, 1H), 3.45 (dd, 2H), 3.34 (dd, 2H)

[0470] <Synthesis of base polymer 11>

[0471]

[0472] Styrene (3.17 g, 30.5 mmol), N-phenylmaleimide (4.22 g, 24.4 mmol), and monomer 3 (2.0 g, 6.09 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated N,N-dimethylformamide (178 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (60.5 mg, 0.24 mmol) was added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was air-cooled to room temperature. The air-cooled reaction solution was added dropwise to methanol (1.78 L) and stirred at room temperature for 20 minutes. The resulting solid was filtered and vacuum-dried. The obtained solid was redissolved in tetrahydrofuran (150 mL), filtered, and rinse-washed with tetrahydrofuran (68 mL). The filtrate was added dropwise to methanol (2.2 L) and stirred at room temperature for 20 minutes. The resulting solid was filtered and vacuum-dried at 50°C for 4 hours to obtain base polymer 11 (6.79 g, yield 72.3%). The molecular weight of the obtained base polymer 11 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (column: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 4900 and the number-average molecular weight Mn was 3000.

[0473] <Synthesis of EO Polymer 11'>

[0474]

[0475] Under a nitrogen atmosphere, base polymer 11 (1.54 g) and compound 2 (433 mg, 1.10 mmol) were dissolved in anhydrous chloroform (50 mL). 4-dimethylaminopyridine (DMAP) (1.34 g, 11.0 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (340 mg, 1.65 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 42 hours. Anhydrous methanol (2.2 mL) was then added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was filtered and rinsed with chloroform (25 mL). The solution was then concentrated using an evaporator until the volume was 36.5 g, and the concentrate was added dropwise to hexane (250 mL). After stirring at room temperature for 20 minutes, the resulting solid was filtered and rinsed with hexane (125 mL). The obtained solid was redissolved in dichloromethane (46 mL), and methanol (184 mL) was slowly added dropwise while stirring the solution. The supernatant was removed, and the residue was washed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:4, 46 mL). The residue was dissolved in dichloromethane (46 mL), filtered, and then rinsed with dichloromethane (46 mL). The solution was concentrated in an evaporator until the volume was 24.5 g, and the concentrate was added dropwise to methanol (182 mL). After stirring at room temperature for 20 minutes, the resulting solid was filtered and rinsed with methanol (90 mL). The obtained solid was vacuum dried at 50°C for 4 hours to obtain EO polymer 11' (1.32 g).

[0476] <Synthesis of EO Polymer 11>

[0477]

[0478] Under a nitrogen atmosphere, EO polymer 11' (650 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (338 mg, 1.07 mmol) were dissolved in deoxygenated tetrahydrofuran (13 mL), then anhydrous ethanol (13 mL) was added, and the mixture was stirred at 50°C for 18 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The resulting solid was redissolved in dichloromethane (11.4 mL) and added dropwise to hexane (170 mL). The resulting solid was filtered and rinsed with hexane (85 mL) to obtain a green solid. After washing, the solid was redissolved in dichloromethane (22 mL), methanol (110 mL) was slowly added while stirring, the supernatant was removed, and the residue was washed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:5, 22 mL). The residue was redissolved in dichloromethane (22 mL), filtered, and then rinsed with dichloromethane (22 mL). The solution was then concentrated in an evaporator until it reached 15.2 g, and the concentrate was added dropwise to methanol (171 mL). The resulting solid was filtered, rinsed with methanol (85 mL), and then vacuum-dried at 50°C for 7 hours to obtain EO polymer 11 (579 mg). The molecular weight of EO polymer 11 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (column: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 30,000, and the number-average molecular weight Mn was 9,000. The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 contained in EO polymer 11 was determined from the ratio of mass extinction coefficients in absorbance measurement using a spectrophotometer, and the content was 34 mass% (9 mol%).

[0479] <Synthesis of Nonlinear Optically Active Compound 5>

[0480]

[0481] Under a nitrogen atmosphere, compound 4 (0.4 g, 0.56 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (186 mg, 0.59 mmol) were dissolved in tetrahydrofuran (10 mL), to which ethanol (20 mL) was added and the mixture was stirred at room temperature for 16 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 5 (480 mg, yield 84.6%).

[0482] The results of the NMR measurement of nonlinear optically active compound 5 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.99 (t, 1H), 7.02-7.58 (m, 15H), 6.93 (s, 2H), 6.74 (d, 1H), 6.37 (d, 1H), 4.96 (s, 2H), 3.83 (d, 4H), 3.76 (t, 2H), 3 .62 (t, 2H), 2.46 (s, 2H), 2.34 (s, 3H), 2.31 (q, 2H), 1.95 (s, 6H), 1.01 (s, 3H), 0.95 (s, 3H), 0.87 (s, 9H), 0.03 (s, 6H)

[0483] <Synthesis of base polymer 12>

[0484]

[0485] Cyclohexyl vinyl ether (3.79 g, 30.0 mmol), N-ethyl maleimide (2.25 g, 18.0 mmol), and N-succinimidyl 3-maleimidopropionate (3.20 g, 12.0 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated N,N-dimethylformamide (35.6 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (59.6 mg, 0.24 mmol) were added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was air-cooled to room temperature. The air-cooled reaction solution was added dropwise to methanol (390 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (195 mL). The obtained solid was redissolved in tetrahydrofuran (160 mL), filtered, and then rinsed with tetrahydrofuran (80 mL). The filtrate was concentrated in an evaporator until it reached 92.0 g. The resulting solution was added dropwise to methanol (1.07 L) and stirred at room temperature for 20 minutes. The resulting solid was filtered off, rinsed with methanol (600 mL), and then vacuum-dried at 50°C for 8 hours to obtain base polymer 12 (6.7 g, yield 72.2%). The molecular weight of the obtained base polymer 12 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 34,000 and the number-average molecular weight Mn was 15,000.

[0486] <Synthesis of EO Polymer 12'>

[0487]

[0488] Under a nitrogen atmosphere, base polymer 12 (1.8 g) and compound 4 (722 mg, 1.02 mmol) were dissolved in anhydrous chloroform (58.5 mL). 4-dimethylaminopyridine (DMAP) (1.24 g, 10.2 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (315 mg, 1.53 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 12.5 hours. Anhydrous methanol (1.9 mL) was then added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was filtered and rinsed with chloroform (30 mL). The filtrate was concentrated to 19.7 g using an evaporator, and the solution was added dropwise to methanol (267 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (130 mL). The filtered material was dissolved in dichloromethane (46 mL), and methanol (300 mL) was added dropwise while stirring, and the mixture was stirred at room temperature for 20 minutes. After removing the supernatant, the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio, 1:6.5) (46 mL). The residue was dissolved in dichloromethane (20 mL), added dropwise to methanol (400 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (205 mL), and then vacuum-dried at 50°C for 8 hours to obtain EO polymer 12' (1.36 g).

[0489] <Synthesis of EO Polymer 12>

[0490]

[0491] Under a nitrogen atmosphere, 550 mg of EO polymer 12' and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (244 mg, 0.77 mmol) were dissolved in tetrahydrofuran (11 mL), to which 11 mL of ethanol was added and the mixture was stirred at 50°C for 15 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The residue was redissolved in dichloromethane (15 mL), added to methanol (150 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (80 mL). The obtained solid was redissolved in dichloromethane (14 mL), and methanol (70 mL) was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:5) (14 mL). The residue was redissolved in dichloromethane (14 mL), filtered, and then rinsed with dichloromethane (14 mL). The filtrate was concentrated in an evaporator until it reached 20.9 g, and the resulting solution was added dropwise to methanol (160 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (80 mL), and then vacuum-dried at 50°C for 8 hours to obtain EO polymer 12 (395 mg). The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 5 in EO polymer 12 was determined from the ratio of mass extinction coefficients measured using a spectrophotometer, and the content was found to be 36 mass% (8 mol%).

[0492] <Synthesis of EO Polymer 13'>

[0493]

[0494] Under a nitrogen atmosphere, base polymer 2 (1.0 g) and compound 4 (399 mg, 0.56 mmol) were dissolved in anhydrous chloroform (35 mL). 4-dimethylaminopyridine (DMAP) (689 mg, 5.6 mmol) and N,N'-diisopropylcarbodiimide (DIC) (130 μL) were added, and the mixture was stirred in an oil bath at 60°C for 40 hours. Then, anhydrous methanol (4.5 mL) and N,N'-diisopropylcarbodiimide (DIC) (86 μL) were added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was filtered and rinsed with chloroform (20 mL). The filtrate was concentrated to 25.8 g using an evaporator, and the solution was added dropwise to methanol (170 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (85 mL). The filtered material was dissolved in dichloromethane (22 mL), and hexane (66 mL) was added dropwise while stirring, and the mixture was stirred at room temperature for 20 minutes. After removing the supernatant, the residue was rinsed with a mixed solution of dichloromethane and hexane (mixing volume ratio, 1:3) (22 mL). The residue was dissolved in dichloromethane (22 mL), filtered, and then rinsed with dichloromethane (22 mL). The filtrate was concentrated in an evaporator to 14.6 g, and the solution was added dropwise to methanol (110 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (55 mL), and then vacuum-dried at 50°C for 8 hours to obtain EO polymer 13' (927 mg).

[0495] <Synthesis of EO Polymer 13>

[0496]

[0497] Under a nitrogen atmosphere, EO polymer 13' (900 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (354 mg, 1.12 mmol) were dissolved in tetrahydrofuran (18 mL), to which ethanol (18 mL) was added and the mixture was stirred at 50°C for 16 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The residue was redissolved in dichloromethane (15 mL), added to hexane (150 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with hexane (75 mL). The obtained solid was redissolved in dichloromethane (22 mL), and methanol (66 mL) was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:3) (22 mL). The residue was redissolved in dichloromethane (22 mL), filtered, and then rinsed with dichloromethane (22 mL). The filtrate was concentrated in an evaporator until it reached 22.2 g, and the resulting solution was added dropwise to methanol (165 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (85 mL), and then vacuum-dried at 50°C for 8 hours to obtain EO polymer 13 (799 mg). The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 5 contained in EO polymer 13 was determined from the ratio of mass extinction coefficients measured by a spectrophotometer, and the content was found to be 35% by mass (7 mol%).

[0498] <Synthesis of Compound 11> Compound 11 was synthesized in the same manner as Compound 4 described in Japanese Patent Publication No. 2019-173032.

[0499]

[0500] <Synthesis of Monomer 4>

[0501]

[0502] Under a nitrogen atmosphere, 4-bromostyrene (10.8 g, 58.8 mmol), tripotassium phosphate aqueous solution (2 M, 73.5 mL, 147 mmol), and dibutylhydroxytoluene (15.1 mg) were added to a solution of compound 11 (16.5 g, 58.8 mmol) in deoxygenated tetrahydrofuran (147 mL), and nitrogen bubbling was performed while stirring at room temperature for 20 minutes. Subsequently, tetrakis(triphenylphosphine)palladium (Pd(PPh) ３ ) ４ (2.04 g, 1.77 mmol) was added and the mixture was stirred at 70°C for 10 hours. After the reaction was complete, the mixture was air-cooled to room temperature and extracted with ethyl acetate (150 mL). The organic layer was washed with water (100 mL) and saturated sodium chloride aqueous solution (100 mL), dried over sodium sulfate, and then filtered. The filtrate was concentrated using an evaporator and purified by silica gel column chromatography to obtain monomer 4 (13.3 g, 88.2%).

[0503] The results of the NMR measurement of monomer 4 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ7.89 (d, 1H), 7.76 (d, 1H), 7.31-7.53 (m, 5H), 7.18 (s, 1H), 6.81 (dd, 1H), 5.83 (d, 1H), 5.30 (d, 1H), 3.45 (dd, 2H), 3.34 (dd, 2H)

[0504] <Synthesis of base polymer 14>

[0505]

[0506] Monomer 4 (963 mg, 3.76 mmol), N-ethylmaleimide (1.41 g, 11.3 mmol), styrene (1.57 g, 15.0 mmol), and N-succinimidyl 3-maleimidopropionic acid (2.0 g, 7.51 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated N,N-dimethylformamide (50 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (37.3 mg, 0.15 mmol) were added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was air-cooled to room temperature. The air-cooled reaction solution was added dropwise to methanol (540 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (280 mL). The obtained solid was redissolved in tetrahydrofuran (60 mL), filtered, and then rinsed with tetrahydrofuran (11 mL). The filtrate was added dropwise to methanol (620 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered off, rinsed with methanol (300 mL), and then vacuum-dried to obtain base polymer 14 (5.1 g, yield 85.1%). The molecular weight of the obtained base polymer 14 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 110,000 and the number-average molecular weight Mn was 27,000.

[0507] <Synthesis of EO Polymer 14'>

[0508]

[0509] Under a nitrogen atmosphere, base polymer 14 (1.0 g) and compound 2 (270 mg, 0.69 mmol) were dissolved in anhydrous chloroform (31.2 mL). 4-dimethylaminopyridine (DMAP) (839 mg, 6.9 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (213 mg, 1.03 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 16.5 hours. Then, anhydrous methanol (1.4 mL) was added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was added dropwise to methanol (440 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (200 mL). The obtained solid was dissolved in dichloromethane (58 mL), filtered, and the filtrate was concentrated using an evaporator until it reached 21.3 g. The obtained solution was added dropwise to methanol (144 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (100 mL), and then vacuum-dried at 50°C for 5 hours to obtain EO polymer 14' (1.0 g).

[0510] <Synthesis of EO Polymer 14>

[0511]

[0512] Under a nitrogen atmosphere, EO polymer 14' (860 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (439 mg, 1.39 mmol) were dissolved in tetrahydrofuran (20 mL), to which ethanol (220 mL) was added and the mixture was stirred at 50°C for 16 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The residue was redissolved in dichloromethane (23 mL), added to methanol (207 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (100 mL). The obtained solid was redissolved in dichloromethane (34 mL), activated clay (900 mg) was added, and the mixture was stirred at room temperature for 30 minutes. The activated clay was then removed by filtration and rinsed with dichloromethane (34 mL). The filtrate was concentrated using an evaporator until it yielded 28.0 g. The resulting solution was added dropwise to methanol (210 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (210 mL), and then vacuum-dried at 50°C for 5 hours to obtain EO polymer 14 (826 mg). The content of the group obtained by removing one hydrogen atom from nonlinear optically active compound 1 in EO polymer 14 was determined from the ratio of mass extinction coefficients measured using a spectrophotometer, and the content was found to be 35% by mass (11 mol%).

[0513] <Synthesis of base polymer 15>

[0514]

[0515] Butyl vinyl ether (3.01 g, 30.0 mmol), N-ethyl maleimide (2.25 g, 18.0 mmol), and N-succinimidyl 3-maleimidopropionate (3.20 g, 12.0 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated N,N-dimethylformamide (35.6 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (59.6 mg, 0.24 mmol) were added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was air-cooled to room temperature. The air-cooled reaction solution was added dropwise to methanol (360 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (180 mL). The obtained solid was redissolved in tetrahydrofuran (150 mL), filtered, and then rinsed with tetrahydrofuran (85 mL). The filtrate was concentrated in an evaporator until it reached 84.5 g. The resulting solution was added dropwise to methanol (590 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered off, rinsed with methanol (300 mL), and then vacuum-dried at 50°C for 8 hours to obtain base polymer 15 (3.5 g, yield 41.4%). The molecular weight of the obtained base polymer 15 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 34,000 and the number-average molecular weight Mn was 15,000.

[0516] <Synthesis of EO Polymer 15'>

[0517]

[0518] Under a nitrogen atmosphere, base polymer 15 (1.8 g) and compound 4 (729 mg, 1.03 mmol) were dissolved in dehydrated chloroform (63.9 mL). 4-dimethylaminopyridine (DMAP) (1.14 g, 10.3 mmol) and N,N'-dicyclohexylcarbodiimide (DCC) (289 mg, 1.40 mmol) were added, and the mixture was stirred in an oil bath at 60°C for 12 hours. Then, dehydrated methanol (1.9 mL) was added, and the mixture was stirred in an oil bath at 60°C for 6 hours. After cooling to room temperature, the reaction solution was filtered and rinsed with chloroform (32 mL). The filtrate was concentrated to 45.5 g using an evaporator, and the solution was added dropwise to methanol (307 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (150 mL). The filtered material was dissolved in dichloromethane (42 mL), and methanol (168 mL) was added dropwise while stirring, and the mixture was stirred at room temperature for 20 minutes. After removing the supernatant, the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio, 1:4) (42 mL). The residue was dissolved in dichloromethane (21 mL), and this was added dropwise to methanol (315 mL), and the mixture was stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (105 mL), and then vacuum-dried at 50°C for 6.5 hours to obtain EO polymer 15' (1.61 g).

[0519] <Synthesis of EO Polymer 15>

[0520]

[0521] Under a nitrogen atmosphere, 550 mg of EO polymer and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile were dissolved in tetrahydrofuran (11 mL) and ethanol (11 mL) was added. The mixture was stirred at 50°C for 15 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The residue was redissolved in dichloromethane (16 mL) and added to methanol (160 mL), then stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (80 mL). The obtained solid was redissolved in dichloromethane (14 mL), and methanol (56 mL) was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:4) (14 mL). The residue was redissolved in dichloromethane (14 mL), filtered, and then rinsed with dichloromethane (14 mL). The filtrate was concentrated in an evaporator until it reached 45.4 g, and the resulting solution was added dropwise to methanol (350 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (170 mL), and then vacuum-dried at 50°C for 8 hours to obtain EO polymer 15 (414 mg). The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 5 contained in EO polymer 15 was determined from the ratio of mass extinction coefficients measured by absorbance measurement using a spectrophotometer, and the content was found to be 33 mass% (7 mol%).

[0522] <Synthesis of base polymer 16>

[0523]

[0524] Phenylmaleimide (6.2 g, 35.8 mmol) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (3.0 g, 11.9 mmol) were dissolved in deoxygenated N,N-dimethylformamide (14.5 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (47.4 mg, 0.19 mmol) was added. After purging with nitrogen, the reaction solution was heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C and stirred for a further 2 hours. The reaction solution was air-cooled, diluted with tetrahydrofuran (184 mL), and then added dropwise to methanol (1.1 L), and stirred at room temperature for 20 minutes. The resulting solid was filtered, dissolved in tetrahydrofuran (184 mL), and filtered. The filtrate was concentrated in an evaporator until it reached 123.4 g. The concentrated solution was added dropwise to methanol (1.42 L) and stirred at room temperature for 20 minutes. The resulting solid was filtered, and the filtered material was rinsed with methanol (0.7 L) and then vacuum-dried at 50°C for 5 hours to obtain base polymer 16 (5.89 g). The molecular weight of the obtained base polymer 16 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (column: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 28,000 and the number-average molecular weight Mn was 9,000.

[0525] <Synthesis of EO Polymer 16>

[0526]

[0527] Under a nitrogen atmosphere, base polymer 16 (300 mg) and nonlinear optically active compound 1 (68 mg, 0.1 mmol) were dissolved in deoxygenated 1,4-dioxane (8.3 mL), stirred at room temperature for 5 minutes, then dibutyltin dilaurate (DBTDL) (32 mg) was added and the mixture was stirred in an oil bath at 110°C for 2 hours. Subsequently, dehydrated methanol (42 μL) was added and the mixture was stirred in an oil bath at 100°C for 1 hour. After the reaction solution was air-cooled, it was added dropwise to methanol (150 mL), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (50 mL) to obtain EO polymer 16 (280 mg). The content of the group obtained by removing one hydrogen atom from nonlinear optically active compound 1 in EO polymer 16 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content was found to be 21% by mass (6 mol%).

[0528] <Synthesis of Compound 12> Compound 12, described below, was synthesized in the same manner as compound 4 described in Macromolecules, 2015, 48, 2849-2854.

[0529]

[0530] <Synthesis of Compound 13>

[0531]

[0532] Under a nitrogen atmosphere, compound 12 (802 mg, 3.4 mmol) and 4-dimethylaminopyridine (DMAP) (103 mg, 0.85 mmol) were added to a solution of compound 4 (2.0 g, 2.82 mmol) in dichloromethane (20 mL), and the mixture was cooled to 0°C. Then, a solution of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl) (648 mg, 3.4 mmol) in anhydrous dichloromethane (6.0 mL) was added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred for 6 hours. After the reaction was complete, water (100 mL) was added to the solution and extracted with ethyl acetate (150 mL). The organic layer was washed with saturated sodium bicarbonate aqueous solution (100 mL) and Brine (100 mL), dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain compound 13 (2.01 g, yield 76.8%).

[0533] <Synthesis of Compound 14>

[0534]

[0535] A solution of compound 13 (2.6 g, 2.8 mmol) in tetrahydrofuran (45 mL) was cooled to 0°C, and aqueous hydrogen chloride solution (4 M, 21 mL, 84 mmol) was added dropwise. After addition, the temperature was raised to room temperature and the mixture was stirred for 1.5 hours. After the reaction was complete, water (100 mL) was added, the mixture was neutralized with aqueous sodium bicarbonate solution, and extracted with ethyl acetate (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain compound 14 (1.89 g, yield 82.9%).

[0536] The results of the NMR measurement of compound 14 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ10.06 (d, 1H), 7.48 (d, 1H), 7.14-7.32 (m, 8H), 6.93 (s, 2H), 6.49 (s, 3H), 6.30 (d, 1H), 5.26 (s, 2H), 4.97 (s, 2H), 4.33 (s, 2H), 3.86 (dt, 4H), 3.73 (dt, 4H), 2.86 (s, 2H), 2.77 (d, 2H), 2.73 (s, 2H), 2.41 (s, 2H), 2.34 (s, 3H), 1.97 (s, 6H), 1.05 (s, 6H)

[0537] <Synthesis of Nonlinear Optically Active Compound 6>

[0538]

[0539] Under a nitrogen atmosphere, a solution of compound 14 (250 mg, 0.31 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (101 mg, 0.32 mmol) in tetrahydrofuran (12.5 mL) was mixed with ethanol (12.5 mL) and stirred at room temperature for 16 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 6 (180 mg, yield 52.8%).

[0540] The results of the NMR measurement of nonlinear optically active compound 6 are shown below.１ H-NMR (400MHz, CDCl ３ )δ7.78(t,1H),7.47-7.58(m,6H),7 .28-7.36 (m, 5H), 7.18 (s, 2H), 6.94 ( s, 2H), 6.75 (d, 1H), 6.75 (d, 1H), 6.4 9 (t, 2H), 6.43 (d, 1H), 5.24 (s, 2H), 4 .91 (s, 2H), 4.31 (s, 2H), 3.68-3.91 (m, 8H), 2.87 (q, 2H), 2.72 (t, 2H), 2.4 4 (s, 2H), 2.35 (s, 3H), 2.23 (q, 2H), 1.95 (s, 6H), 1.00 (s, 3H), 0.92 (s, 3H)

[0541] <ベースポリマー17の synthesis>

[0542]

[0543] Styrene (3.91 g, 37.6 mmol) and N-succinimidyl 3-maleimidopropionate (10.0 g, 37.6 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated DMF (234 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (74.6 mg, 0.30 mmol) were added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was air-cooled to room temperature. The air-cooled reaction solution was added dropwise to methanol (2.34 L), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (0.5 L) and then tert-butyl methyl ether (0.5 L), and then vacuum-dried. The dried solid was redissolved in tetrahydrofuran (162 mL), filtered, and then rinsed with tetrahydrofuran (162 mL). The filtrate was added dropwise to tert-butyl methyl ether (3.24 L), and the resulting solid was filtered off. The filtered solid was rinsed with tert-butyl methyl ether (600 mL) and vacuum dried to obtain base polymer 17 (9.58 g, yield 65.1%). The molecular weight of the obtained base polymer 17 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: 0.5 wt% LiBr in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 66,000 and the number-average molecular weight Mn was 16,000.

[0544] <Synthesis of EO Polymer 17'>

[0545]

[0546] Under a nitrogen atmosphere, base polymer 17 (517 mg) and compound 14 (500 mg, 0.61 mmol) were dissolved in anhydrous chloroform (14 mL). 4-dimethylaminopyridine (DMAP) (750 mg, 6.14 mmol) and N,N'-diisopropylcarbodiimide (DIC) (141 μL) were added, and the mixture was stirred in an oil bath at 35°C for 8 hours. Then, a solution of 9-(hydroxymethyl)anthracene (255 mg, 1.22 mmol) in anhydrous chloroform (0.8 mL) was added, and the mixture was stirred in a water bath at 35°C for 48 hours. Subsequently, anhydrous methanol (5.0 mL) and N,N'-diisopropylcarbodiimide (DIC) (74 μL) were added, and the mixture was stirred in an oil bath at 35°C for 6 hours. After air cooling to room temperature, the reaction solution was filtered and rinsed with chloroform (14 mL). The filtrate was concentrated in an evaporator to 16.3 g, and the solution was added dropwise to methanol (110 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with methanol (55 mL). The filtered material was dissolved in dichloromethane (16 mL), and hexane (48 mL) was added dropwise while stirring, and the mixture was stirred at room temperature for 20 minutes. After removing the supernatant, the residue was rinsed with a mixed solution of dichloromethane and hexane (mixing volume ratio 1:3) (16 mL). The residue was dissolved in dichloromethane (16 mL), filtered, and then rinsed with dichloromethane (16 mL). The filtrate was concentrated in an evaporator to 16.3 g, and the solution was added dropwise to methanol (110 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (55 mL), and then vacuum-dried at 40°C for 5 hours to obtain EO polymer 17' (685 mg).

[0547] <Synthesis of EO Polymer 17>

[0548]

[0549] Under a nitrogen atmosphere, EO polymer 17' (340 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (183 mg, 0.58 mmol) were dissolved in tetrahydrofuran (6.8 mL), to which ethanol (6.8 mL) was added and the mixture was stirred at 35°C for 15 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator. The residue was redissolved in dichloromethane (15 mL), added to hexane (60 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered and rinsed with hexane (60 mL). The obtained solid was redissolved in dichloromethane (8.0 mL), and methanol (24 mL) was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:3) (24 mL). The residue was redissolved in dichloromethane (8.0 mL), filtered, and then rinsed with dichloromethane (8.0 mL). The filtrate was concentrated in an evaporator until it reached 7.5 g, and the resulting solution was added dropwise to methanol (56 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, rinsed with methanol (56 mL), and then vacuum-dried at 40°C for 4 hours to obtain EO polymer 17 (199 mg). The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 6 in EO polymer 17 was determined from the ratio of mass extinction coefficients measured using a spectrophotometer, and the content was found to be 49% by mass.

[0550] <Evaluation Equipment> The following equipment was used for the evaluation below. TG-DTA: Differential calorimetry simultaneous measurement device STA-200 manufactured by Hitachi High-Tech Corporation DSC: Differential scanning calorimeter DSC-60APlus manufactured by Shimadzu Corporation Vacuum constant temperature drying oven: DP-23 manufactured by Yamato Scientific Co., Ltd.

[0551] (Example 1) <Heat drying process for solvent and moisture removal> The EO polymer 1 synthesized as described above was dried in a vacuum constant-temperature dryer at 110°C for 3 hours.

[0552] <Quantitative Evaluation of Residual Solvent and Moisture Content by TG-DTA and Evaluation of Decomposition Temperature> The EO polymer 1 that underwent the above heat drying process was weighed into an aluminum pan (product name "Al open-type sample container, Φ5.2 H2.5 mm", manufactured by Hitachi High-Tech Science Corporation), and the temperature was raised to 400°C at 10°C / min. The TG-DTA was measured to confirm the mass loss. As a result, the mass loss up to 180°C was 0.3%. The temperature at which a 5% mass loss occurred when the temperature was raised further was 299°C, and above this temperature, a significant mass loss due to the decomposition of the dye or polymer was observed. Normally, a mass loss of 0.5% or less is considered to be due to moisture adsorption during the evaluation procedure, etc., and not a mass loss due to residual solvent or moisture in the compound. Therefore, this measurement suggests that the EO polymer 1 that underwent the above heat drying process does not contain residual components such as solvent or moisture and is sufficiently dried. The results are shown in Table 3.

[0553] <Evaluation of Filterability> The EO polymer 1 that underwent the above heat drying process was weighed to a solid content concentration of 13% by mass and dissolved in cyclohexanone. The resulting cyclohexanone solution was filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm. As a result, the time required to filter 0.2 ml of the cyclohexanone solution was less than 5 seconds. This measurement suggests that viscosity increase and gelation due to the heat drying process were suppressed in EO polymer 1. In the evaluation of filterability, the time required to filter 0.2 ml of the cyclohexanone solution was evaluated as "A" if it was less than 5 seconds, "B" if it took 5 seconds or more, and "C" if no liquid passed through. The results are shown in Table 3.

[0554] (Example 2) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 2. The results are shown in Table 3. The mass loss up to 180°C was 0.3%, indicating sufficient drying, and the filtration performance was also good.

[0555] (Example 3) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 3. The results are shown in Table 3. The mass loss up to 180°C was 0.5%, indicating sufficient drying, and the filtration performance was also good.

[0556] (Comparative Example 1) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 4. The results are shown in Table 3. The mass loss up to 180°C was 0.4%, indicating sufficient drying, but the filtration performance was worse compared to when EO polymer 1, EO polymer 2, and EO polymer 3 were used.

[0557] (Comparative Example 2) The same evaluation as in Comparative Example 1 was performed, except that the drying temperature and time were changed to 85°C and 3 hours. The results are shown in Table 3. The mass loss up to 180°C was 0.4%, and it is considered that drying was sufficient with no residual solvent, etc. However, the filterability was worse compared to when EO polymer 1, EO polymer 2, and EO polymer 3 were used.

[0558] (Comparative Example 3) The same evaluation as in Comparative Example 1 was performed, except that the drying temperature and time were changed to 80°C and 6 hours. The results are shown in Table 3. The mass loss up to 180°C was 0.5%, and although there was some residual solvent, drying was sufficient and filterability was ensured.

[0559] (Comparative Example 4) The same evaluation as in Comparative Example 1 was performed, except that the drying temperature and time were changed to 50°C and 8 hours. The results are shown in Table 3. The mass loss up to 180°C was 1.1%, and residual solvent etc. was observed, indicating insufficient drying, but the filterability was ensured.

[0560]

[0561] As described above, when using the comparative example polymer compound (EO polymer 4), there was an upper limit to the drying temperature and a long drying time was required to satisfy the conditions for removing residual solvent and ensuring filtration. In contrast, the polymer compounds of the examples (EO polymer 1, EO polymer 2, and EO polymer 3) were found to have a higher upper limit to the drying temperature and good filtration. Furthermore, the thermal decomposition temperature (temperature of 5% mass loss) of the polymer compounds of the examples was nearly 20°C higher for EO polymer 1, nearly 65°C higher for EO polymer 2, and nearly 30°C higher for EO polymer 3 than the thermal decomposition temperature of the comparative example polymer compound, indicating that the thermal durability of the polymer compounds according to the embodiment of the present invention has been greatly improved.

[0562] (Example 4) <Preparation of composition for thick film> EO polymer 2 was weighed to a solid content concentration of 7% by mass, dissolved in dibromo methane, and filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.5 μm to obtain a composition for thick film. 0.2 ml of the above composition was dropped onto a 100 mm square glass substrate washed with ultrapure water, and the composition for thick film was coated onto the glass substrate using an Adjustable Applicator (coating width 50 mm) manufactured by BEVS INDUSTRIAL Co. Limited, with the gap between the substrate and the blade set to 200 μm.

[0563] <Preparation of Thick Film and Observation of Film State> A glass substrate coated with the above composition was left to dry at room temperature to obtain a film with a thickness of 28 μm. The state of the obtained film was visually inspected and evaluated as "a" if there were no defects in the film formation, such as cracks or delamination, and "b" if there were defects. The results are shown in Table 4.

[0564] <Measurement of Glass Transition Temperature> EO polymer 2 was weighed into an aluminum pan (product name "Al Crimp Cell AUS", manufactured by Shimadzu Corporation), covered with an aluminum lid (product name "Al CRIMMP PAN AUS", manufactured by Shimadzu Corporation), and the glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC) (product name "DSC-60APlus", manufactured by Shimadzu Corporation). Tg was defined as the temperature corresponding to the intersection of the baseline and 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 10°C / min. The results are shown in Table 4.

[0565] (Comparative Example 5) A thick film composition with a solid content of 8% by mass was prepared using EO polymer 5 instead of EO polymer 2, and a thick film was prepared in the same manner as in Example 4, except that the gap between the substrate and the blade was changed to 150 μm. The thickness of the prepared film was 23 μm, and the condition of the film was visually confirmed. The results are shown in Table 4.

[0566]

[0567] As shown in Table 4, while the glass transition temperatures were similar in Example 4 and Comparative Example 5, the film of Comparative Example 5 had numerous cracks on its surface, whereas the film of Example 4 showed no defects even when made into a thick film, clearly indicating that the film's fragility had been improved.

[0568] (Example 5) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 6. The results are shown in Table 5. The mass loss up to 180°C was 0.2%, indicating sufficient drying, and the filtration performance was also good.

[0569] (Example 6) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 7. The results are shown in Table 5. The mass loss up to 180°C was 0.3%, indicating sufficient drying, and the filtration performance was also good.

[0570] (Example 7) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 8. The results are shown in Table 5. The mass loss up to 180°C was 0.2%, indicating sufficient drying, and the filtration performance was also good.

[0571] (Example 8) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 9. The results are shown in Table 5. The mass loss up to 180°C was 0.4%, indicating sufficient drying, and the filtration performance was also good.

[0572] (Example 9) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 10. The results are shown in Table 5. The mass loss up to 180°C was 0.4%, indicating sufficient drying, and the filtration performance was also good.

[0573] (Example 10) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 11. The results are shown in Table 5. The mass loss up to 180°C was 0.4%, indicating sufficient drying, and the filtration performance was also good.

[0574] (Example 11) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 12. The results are shown in Table 5. The mass loss up to 180°C was 0.3%, indicating sufficient drying, and the filtration performance was also good.

[0575] (Example 12) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 13. The results are shown in Table 5. The mass loss up to 180°C was 0.7%, indicating sufficient drying, and the filtration performance was also good.

[0576] (Comparative Example 6) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 16. The results are shown in Table 5. The mass loss up to 180°C was 1.1%, and residual solvent etc. was observed, indicating insufficient drying and a deterioration in filterability.

[0577]

[0578] As shown in Table 5, it was found that when the comparative polymer compound (EO polymer 16) was used, residual solvent could not be removed under the same drying conditions, or even if residual solvent could be removed, filtration could not be guaranteed. In contrast, it was found that the polymer compounds of the examples (EO polymers 6 to 13) had a higher upper limit of drying temperature and good filtration. Furthermore, the thermal decomposition temperature (temperature of 5% mass loss) of the polymer compounds of the examples was higher than that of the polymer compound of Comparative Example 6 (EO polymer 16), indicating that the thermal durability of the polymer compounds according to the embodiment of the present invention was greatly improved.

[0579] (Example 14) A thick film composition with a solid content of 8% by mass was prepared using EO polymer 10 instead of EO polymer 2, and a thick film was prepared in the same manner as in Example 4, except that the gap between the substrate and the blade was changed to 100 μm. The thickness of the prepared film was 20 μm, and the condition of the film was visually confirmed. The results are shown in Table 6.

[0580] (Example 15) A thick film composition with a solid content of 8% by mass was prepared using EO polymer 13 instead of EO polymer 2, and a thick film was prepared in the same manner as in Example 4. The thickness of the prepared film was 26 μm, and the condition of the film was visually confirmed. The results are shown in Table 6.

[0581] (Comparative Example 7) A thick film composition with a solid content of 8% by mass was prepared using EO polymer 16 instead of EO polymer 2, and a thick film was prepared in the same manner as in Example 4, except that the gap between the substrate and the blade was changed to 150 μm. The thickness of the prepared film was 26 μm, and the condition of the film was visually confirmed. The results are shown in Table 6.

[0582]

[0583] As shown in Table 6, while the glass transition temperatures of Examples 14 and 15 were similar to or higher than those of Comparative Example 7, the film of Comparative Example 7 had numerous cracks on its surface, whereas the films of Examples 14 and 15 showed no defects even when made into thick films, clearly indicating an improvement in the film's fragility.

[0584] The polymer compounds according to the embodiments of the present invention exhibit suppressed viscosity increase and gelation during heating, and have excellent thermal stability, making them suitable for use in nonlinear optical elements or optical modulators equipped therewith.

[0585] Although various embodiments have been described above, it goes without saying that the present invention is not limited to these examples. It is clear to those skilled in the art that various modifications and variations can be conceived, and these will naturally fall within the technical scope of the present invention. Furthermore, the components in the above embodiments may be combined in any way without departing from the spirit of the invention.

[0586] This application is based on the Japanese Patent Application No. 2025-009460, No. 2025-009461, No. 2025-009462, No. 2025-048742, No. 2025-048743, and No. 2025-048744, both filed on January 22, 2025, and their contents are incorporated by reference within this application.

Claims

1. A polymer compound containing at least one selected from the group consisting of a repeating unit represented by the following formula (1-1), a repeating unit represented by the following formula (1-2), and a repeating unit represented by the following formula (1-3). [In formula (1-1), R １１１ ~R １１３ are each independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, or a halogen atom, L １１１ and L １１２ each independently represent a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group group A which may have a substituent, X １１１ is a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), Y １１１ and Y １１２ are each independently an oxygen atom or N-Z １１１ where Z １１１ is a hydrogen atom, a group selected from the following hydrocarbon group group A which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent, n １１１ represents 0 to 1. ] [In formula (1-2), R １２１ and R １２２ each independently represent a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, or a halogen atom, L １２１ each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group group A which may have a substituent, or a divalent aromatic group which may have a substituent, X １２１ is a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), n １２１ is an integer from 1 to 5. ] [In formula (1-3), R １３１ ~R １３３ each independently represent a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, or a halogen atom, R １３４ Each of these is independently a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, n １３２ If the number is 2 or more, the R １３４ is another R １３４ It may also be bonded to form a ring, R １３５ Each is independently a single bond, an optionally substituted divalent alkyl group, an optionally substituted divalent aromatic group, or an optionally substituted divalent aralkyl group, X １３１ Each of these is independently a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), n １３１ n is an integer between 1 and 5. １３２ n is an integer between 0 and 4, where n １３１ to n １３２ The sum of the numbers is 5 or less. [In formula (2), Ar ２１ Each of these is independently a divalent aromatic group which may have substituents, and R ２１ and R ２３ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A, which may have substituents, or a divalent aromatic group which may have substituents, and R ２２ and R ２４ Each independently represents a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ２１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ２１ This is a group represented by the following formula (3), and m ２１ Each of these is an integer between 0 and 5, and m ２２ m is an integer between 1 and 5. ２３ n is an integer between 0 and 5. ２１ [This is an integer between 1 and 15.] [In formula (3), *J ３１ Y ２１ This represents the bonding position with R ３１ and R ３２ Each independently represents a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, R ３１ and R ３２ They may be bonded together to form a ring, or R ３１ and R ３２ R ３１ and R ３２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ３３ ~R ３５ Each independently represents a cyano group, a C2-C30 alkyloxycarbonyl group which may have substituents, or a C1-C30 alkylsulfonyl group which may have substituents, X ３１ is an oxygen atom, a sulfur atom, or N-Q ３１ This represents Q ３１ represents a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. ] <Hydrogen group A> A branched, linear or cyclic alkyl group having 1 to 30 carbon atoms, a branched, linear or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, linear or cyclic alkynyl group having 2 to 30 carbon atoms, in which part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group and / or a silicon atom.

2. Y in equation (2) above ２１ At least one of them is independently represented by the following formula (4), where n in formula (2) is ２１ If the number is 2 or more, the Y ２１ R inside ４１ and R ４２ is, other Y ２１ R included ４１ or R ４２ The polymer compound according to claim 1, which may be linked to form a ring. [In formula (4), R ４１ and R ４２ Each independently represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ４１ and R ４２ They may be joined together to form a ring.

3. Y in the formula (2) ２１ At least one of them is independently represented by the following formula (5), the following formula (6), or the following formula (7), provided that n in the formula (2) ２１ is 2 or more, R in the Y ２１ , R ５１ , R ５２ , R ６１ , R ６２ , and R ７１ to R ７７ may be linked to R ２１ included in other Y ５１ , R ５２ , R ６１ , R ６２ , or R ７１ to R ７７ to form a ring, The polymer compound according to claim 1. [In formula (5), R ５１ and R ５２ 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, 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, and R ５１ and R ５２ may be bonded to form a ring. ] [In formula (6), R ６１ and R ６２ 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, 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, and R ６１ and R ６２ may be bonded to form a ring, X ６１ represents an oxygen atom, a sulfur atom or N-Q ６１ , Q ６１ This represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group. [In formula (7), R ７１ ~R ７７ Each independently represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ７１ ~R ７７ At least two of them may be joined together to form a ring.

4. Containing the repeating unit represented by the formula (1-1), R in the formula (1-1) １１１ is a methyl group, R １１２ to R １１３ are hydrogen atoms, and the polymer compound according to claim 1.

5. The polymer compound according to claim 1, further comprising a repeating unit represented by the following formula (8). [In formula (8), R ８１ and R ８２ Each independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom, L ８１ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, Y ８１ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a heterocyclic group which may have substituents, or a hydroxyl group, n ８１ [This is an integer between 0 and 10.] 6. The polymer compound according to claim 1, further comprising a repeating unit represented by the following formula (9). [In formula (9), A ９１ A represents a trivalent group obtained by removing two hydrogen atoms from a group selected from the hydrocarbon group A, which may have substituents. ９２ Each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, and L ９１ Each independently represents a single bond, a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, R ９１ n represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, ９１ n is an integer between 0 and 5. ９２ [This is an integer between 0 and 1.] 7. A in formula (9) above ９１ The polymer compound according to claim 6, wherein is represented by the following formula (10). [In formula (10), R １０１ ~R １０３ Each of these independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom. *J １０１ is, L ９１ or R ９１ This indicates the bonding position with *J １０２ *J represents the connection position with adjacent repeating units. １０３ is, A ９２ This indicates the connection position with or with an adjacent repeating unit.

8. The polymer compound according to claim 1, further comprising a repeating unit represented by the following formula (11). [In formula (11), R １１１１ ~R １１１６ Each of these is independently a group selected from the hydrocarbon group A, which may have a hydrogen atom or a substituent, and L １１１１ and L １１１２ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, Y １１１１ and Y １１１２ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, a hydroxyl group which may have substituents, or a silyl group which may have substituents, and R １１１３ ~R １１１６ , L １１１１ and L １１１２ At least two of them may be joined together to form a ring, n １１１１ and n １１１２ Each of these is an integer between 0 and 5, independently of the others.

9. A composition comprising a polymer compound according to any one of claims 1 to 8 and an organic solvent.

10. A nonlinear optical element comprising a film containing a polymer compound according to any one of claims 1 to 8.

11. The nonlinear optical element according to claim 10, which operates based on the electro-optic effect.

12. An optical modulator comprising the nonlinear optical element described in claim 10.

Images