Compounds, polymer compounds, compositions, nonlinear optical elements, and optical modulators

Abstract

To provide compounds and polymer compounds that exhibit a higher electro-optic effect in the shorter wavelength band than the C-band compared to dyes with similar maximum absorption wavelengths, and to provide a nonlinear optical element using the compound or polymer compound, and an optical modulator equipped with the nonlinear optical element that operates based on the electro-optic effect. [Solution] A compound represented by the following formula (1). [Formula 1] TIFF2026169001000098.tif43166 [The definition of the base in formula (1) is as described in the specification.]

Description

[Technical Field]

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

[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 are materials that exhibit a polarization response proportional to the square, cube, or higher-order terms of the magnitude of the electric field of light. Those that produce a second-order nonlinear optical effect, such as the first-order electro-optic effect (Pockels 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. Nonlinear optical materials are desirable to have a high EO coefficient, high heat resistance, and low absorption loss at wavelengths used for optical communication (Patent Documents 1-4). In particular, since the performance of each dye molecule greatly affects the figure of merit r33 and absorption loss of the entire EO polymer, there is a need for dye molecule design guidelines that can achieve both high r33 and low absorption loss, that is, improve the figure of merit while maintaining the absorption wavelength.

[0004] Conventional development of organic nonlinear optical materials has been based on the premise of use in the C-band (wavelength range of 1530-1565 nm), where absorption loss in optical fibers is low. In recent years, in order to expand the application technology and improve the functionality of organic nonlinear optical materials, it has become necessary to develop organic nonlinear optical materials that are highly efficient in even shorter wavelength bands than the C-band, that is, organic nonlinear optical materials with low absorption loss and large electro-optic effects.

[0005] Patent Document 5 discloses a polymer represented by the following formula as an example of an organic nonlinear optical material that can be suitably used in optical control elements useful in wavelengths shorter than the C band. The polymer below has very low absorption loss in wavelengths shorter than the C band and can be suitably used in optical control elements. On the other hand, a challenge is that the electro-optic effect per dye molecule is low because the π-conjugated chain of the dye is short and the polarization is small. Therefore, from the viewpoint of increasing the efficiency and saving energy of the element, there is a need to develop a material that can further improve the figure of merit r33 per dye molecule while maintaining low absorption loss, that is, while maintaining the maximum absorption wavelength.

[0006] [ka] [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2019 / 151318 [Patent Document 2] Japanese Patent Publication No. 2010-066325 [Patent Document 3] International Publication No. 2011 / 024774 [Patent Document 4] Japanese Patent Publication No. 2015-178544 [Patent Document 5] International Publication No. 2023 / 021921 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] The object of the present invention is to provide compounds and polymer compounds that exhibit higher electro-optic effects in wavelengths shorter than the C-band compared to dyes with similar maximum absorption wavelengths. Another object of the present invention is to provide a nonlinear optical element using the compound or polymer compound, and an optical modulator comprising the nonlinear optical element that operates based on the electro-optic effect. [Means for solving the problem]

[0009] In view of the above problems, the inventors conducted extensive research and found that by introducing an aromatic hydrocarbon group or an aromatic heterocyclic group between the electron-withdrawing group and the π-conjugated chain in the compound structure, a higher figure of merit r33 per molecule of dye can be obtained compared to compounds having a similar maximum absorption wavelength, thus completing the present invention.

[0010] The purpose of this invention is as follows:

[0011] One aspect of the present invention is: This relates to the compound represented by the following formula (1).

[0012] [ka]

[0013] [In formula (1), Ar 11 Each of these is independently a divalent aromatic group which may have substituents, R 11 and R 13 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. R 12 and R 14 Each of these is independently a hydrogen atom, a group selected from the following optionally substituted hydrocarbon group A, an optionally substituted aromatic group, an optionally substituted amino group, a hydroxyl group, or a halogen atom. Y 11 Each is independently a divalent π-conjugated linkage group which may have substituents, where Y 11at least one of is an optionally substituted vinylene group, S 11 is an optionally substituted divalent aromatic group, Z 11 is a group represented by the following formula (2), m 11 each independently represent an integer of 0 to 5, m 12 represents an integer of 1 to 5, m 13 represents an integer of 0 to 5, n 11 represents an integer of 1 to 15.]

[0014]

Chemical Formula

[0015] [In formula (2), *J 21 is the bonding position with S 11 , R 21 and R 22 each independently represent a group selected from the following hydrocarbon group group A which may have a substituent, or an optionally substituted aromatic group, R 21 and R 22 may be bonded to each other to form a ring, or R 21 and R 22 may form a carbonyl group together with R 21 , R 22 and the carbon atom to which they are bonded, R 23 and R 24 each independently represent a cyano group, an optionally substituted alkyloxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted alkylsulfonyl group having 1 to 10 carbon atoms, X 21 is an oxygen atom, a sulfur atom or N-Q 21 , Q 21This is 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, wherein part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom.

[0016] Aspect 2 of the present invention is the compound of Aspect 1, S in equation (1) above 11 However, this relates to compounds that are divalent aromatic groups having 3 to 10 carbon atoms, which may have substituents.

[0017] Aspect 3 of the present invention is a compound of aspect 1 or 2, Y in equation (1) above 11 At least one of them is independently represented by the following equation (3), where n in equation (1) is 11 If it is 2 or more, then R in equation (3) below 31 and R 32 is, other Y 11 R included 31 or R 32 This relates to compounds that may be linked to form a ring.

[0018] [ka]

[0019] [In formula (3), R 31 and R 32 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 31 and R 32 They may be joined together to form a ring.

[0020] Aspect 4 of the present invention is a compound in any one of aspects 1 to 3, Y in equation (1) above 11 However, each can be expressed independently by the following equations (4), (5), or (6): Y 11 At least one of them is expressed by the following equation (4): However, n in formula (1) above 11 If it is 2 or more, Y 11 R inside 41 , R 42 , R 51 , R 52 , and R 61 ~R 67 is, other Y 11 R included 41 , R 42 , R 51 , R 52 , or R 61 ~R 67 This relates to compounds that may be linked to form a ring.

[0021] [ka]

[0022] [In formula (4), R 41 and R 42 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 41 and R 42 They may be joined together to form a ring.

[0023] [ka]

[0024] [In formula (5), R 51and R 52 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 51 and R 52 They may be bonded together to form a ring. X 51 is an oxygen atom, a sulfur atom, or NQ 51 And, Q 51 This is 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 which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, or a boryl group which may have substituents.

[0025] [ka]

[0026] [In formula (6), R 61 ~R 67 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 61 ~R 67 At least two of them may be joined together to form a ring.

[0027] Embodiment 5 of the present invention is a compound in any one of embodiments 1 to 4, n in equation (1) above 11 This concerns compounds where the integer is between 2 and 5.

[0028] Aspect 6 of the present invention is, This invention relates to a composition comprising one of the compounds described in embodiments 1 to 5 and a polymer material.

[0029] Aspect 7 of the present invention is the composition of aspect 6, The present invention relates to a composition in which the polymer material is at least one selected from the group consisting of poly(meth)acrylic acid ester, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, and copolymers thereof.

[0030] Aspect 8 of the present invention is the composition of aspect 6 or 7, This relates to a composition containing an organic solvent.

[0031] Aspect 9 of the present invention is This invention relates to a nonlinear optical element comprising one of the compounds described in embodiments 1 to 5.

[0032] Aspect 10 of the present invention relates to the nonlinear optical element of Aspect 9, This relates to a nonlinear optical element that operates based on the electro-optic effect.

[0033] Aspect 11 of the present invention is This invention relates to an optical modulator comprising a nonlinear optical element according to embodiment 9 or 10.

[0034] Aspect 12 of the present invention is: This invention relates to a polymer compound comprising a group obtained by removing at least one hydrogen atom from the compound represented by the following formula (1), as at least one selected from the substituent and the main chain.

[0035] [ka]

[0036] [In formula (1), Ar 11 Each of these is independently a divalent aromatic group which may have substituents, R 11 and R 13are each independently 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, R 12 and R 14 are each independently a hydrogen atom, a group selected from the following hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, an amino group which may have a substituent, a hydroxy group, or a halogen atom, Y 11 are each independently a divalent π-conjugated linking group which may have a substituent, provided that at least one of Y 11 is a vinylene group which may have a substituent, S 11 is a divalent aromatic group which may have a substituent, Z 11 is a group represented by the following formula (2), m 11 are each independently an integer of 0 to 5, m 12 is an integer of 1 to 5, m 13 is an integer of 0 to 5, n 11 is an integer of 1 to 15.]

[0037]

Chemical Formula

[0038] [In formula (2), *J 21 is the bonding position to S 11 , R 21 and R 22 are each independently a group selected from the following hydrocarbon group group A which may have a substituent, or an aromatic group which may have a substituent, R 21 and R 22 may be bonded to each other to form a ring, or R 21 and R 22 are R 21 and R 22and these may form a carbonyl group together with the carbon atom to which they are bonded, R 23 and R 24 are each independently a cyano group, an optionally substituted alkyloxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted alkylsulfonyl group having 1 to 10 carbon atoms, X 21 is an oxygen atom, a sulfur atom or N-Q 21 , Q 21 is a hydrogen atom, a group selected from the following hydrocarbon group group A which may have a substituent, or an optionally substituted aralkyl group.] <Hydrocarbon Group Group A> A branched, chain or cyclic alkyl group having 1 to 30 carbon atoms, a branched, chain or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, chain or cyclic alkynyl group having 2 to 30 carbon atoms, in which a part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group and / or a silicon atom.

[0039] Aspect 13 of the present invention is the polymer compound according to Aspect 12, wherein the group obtained by removing at least one hydrogen atom from the compound represented by the formula (1) is a group obtained by removing a hydrogen atom from R 14 , relating to the polymer compound.

[0040] Aspect 14 of the present invention relates to a nonlinear optical element comprising the polymer compound according to Aspect 12 or 13.

[0041] Aspect 15 of the present invention relates to the nonlinear optical element according to Aspect 14, which operates based on an electro-optic effect. , relating to the nonlinear optical element.

[0042] Aspect 16 of the present invention relates to an optical modulator comprising the nonlinear optical element according to Aspect 14 or 15. Effects of the Invention

[0043] According to the present invention, it is possible to provide compounds and polymer compounds that exhibit higher electro-optic effects in wavelengths shorter than the C-band compared to dyes with similar maximum absorption wavelengths. Furthermore, according to the present invention, it is possible to provide a nonlinear optical element using the compound or the polymer compound, and an optical modulator equipped with the nonlinear optical element that operates based on the electro-optic effect. [Brief explanation of the drawing]

[0044] [Figure 1] Figure 1 shows the distribution of the maximum absorption wavelength and electro-optic coefficient (EOMW / mass%) in the examples and comparative examples. [Modes for carrying out the invention]

[0045] Explanation of terms The following is an explanation of the terms used in this specification.

[0046] <Polymer compounds> In this specification, a polymeric compound refers to a compound having a molecular weight of 2000 or more and containing four or more identical repeating units in its molecule. The polymeric compound is not particularly limited, but is preferably a polymer, and may be a homopolymer, block copolymer, random copolymer, alternating copolymer, or graft copolymer, or in any other form. The polymer compounds according to the embodiments of the present invention can be used as polymer compounds having nonlinear optical activity. In this specification, the polymer compounds according to the embodiments of the present invention may be referred to as nonlinear optically active polymer compounds.

[0047] <Copolymer> A copolymer is a polymer compound that contains two or more structural units within its molecule.

[0048] <Substituent> Unless otherwise specified, a substituent is any group, but preferably the substituent group W described below. 1The 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.

[0049] <Substituent group W 1 > Substituent group W 1 This 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, alkylthio 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. Substituent group W 1 Among these, from the viewpoint of improving pigment compatibility, the group consisting of alkyl groups, alkoxy groups, aralkyloxy groups, alkylthio groups, aralkylthio groups, haloalkyl groups, silyl groups, and aralkyl groups is preferred, and the group consisting of alkyl groups, alkoxy groups, haloalkyl groups, and silyl groups is particularly preferred. Substituent group W 1 More specifically, the following structures are examples, from the alkyl group to the bond of adjacent substituents.

[0050] [Alkyl group] Alkyl groups are linear, branched, or cyclic, and have one or more carbon atoms, preferably four or more, usually 24 or fewer, preferably 12 or fewer, more preferably 8 or fewer, and even more preferably 6 or fewer. 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, and the like.

[0051] [Alkenyl group] Alkenyl groups are linear, branched, or cyclic, and typically have two or more carbon atoms, usually 24 or fewer, preferably 12 or fewer. Specific examples include vinyl groups.

[0052] [Alkynyl group] The alkynyl group is linear or branched, usually has two or more carbon atoms, usually 24 or fewer, preferably 12 or fewer. Specific examples include the ethynyl group.

[0053] [Alkyloxy group] 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 groups, ethoxy groups, n-propoxy groups, iso-propoxy groups, n-butoxy groups, iso-butoxy groups, sec-butoxy groups, tert-butoxy groups, n-hexyloxy groups, cyclohexyloxy groups, dodecyloxy groups, adamantyloxy groups, and the like.

[0054] [Aromatic oxy group] Aromatic oxy groups have 4 or more carbon atoms, preferably 5 or more, and usually 36 or fewer, preferably 24 or fewer. Specific examples include phenoxy groups, naphthoxy groups, and pyridyloxy groups.

[0055] [Aralkyloxy group] The aralkyloxy group has 4 or more carbon atoms, preferably 5 or more, and is usually 50 or less, preferably 30 or less. Specific examples include the 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-pentioxyl group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, and 8-phenyl-1-octyloxy group.

[0056] [Alkylthio group] Alkylthio groups have one or more carbon atoms, usually 24 or fewer, preferably 12 or fewer. 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, and the like.

[0057] [Aromatic thio group] Aromatic thio groups have 3 or more carbon atoms, preferably 4 or more, and usually 50 or fewer, preferably 30 or fewer. Specifically, examples include phenylthio groups, naphthylthio groups, and pyridylthio groups.

[0058] [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.

[0059] [Alkyloxycarbonyl group] Alkyloxycarbonyl groups have two or more carbon atoms, usually 24 or fewer, and preferably 12 or fewer. Specific examples include methoxycarbonyl groups and ethoxycarbonyl groups.

[0060] [Dialkylamino group] A dialkylamino group has two or more carbon atoms, usually 24 or fewer, and preferably 12 or fewer. Specific examples include dimethylamino group and diethylamino group.

[0061] [Amino group] The amino group may have substituents, preferably a secondary amino group, 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, di-n-butylamino group, methylphenylamino group, ethylphenylamino group, butylphenylamino group, hexylphenylamino group, diphenylamino group, 2,6-dimethylphenylphenylamino group, and 2,4,6-trimethylphenylphenylamino group.

[0062] [Halogen atom] Halogen atoms are typically fluorine, chlorine, bromine, or iodine atoms. More preferably, they are fluorine atoms.

[0063] [haloalkyl group] The haloalkyl group has one or more carbon atoms, usually 12 or fewer, and preferably 6 or fewer. Specific examples include the trifluoromethyl group and the chloromethyl group, with the trifluoromethyl group being more preferred.

[0064] [Silicone group] The silyl group typically has 2 or more carbon atoms, preferably 3 or more, and typically 36 or fewer carbon atoms, preferably 24 or fewer. Specific examples include the trimethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, and triphenylsilyl group.

[0065] [Siloxy group] The siloxy group has 2 or more carbon atoms, preferably 3 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.

[0066] [Aralkyl group] The aralkyl group typically has 7 or more carbon atoms, preferably 9 or more, typically 30 or less, preferably 18 or less, and more preferably 10 or less. Specific examples include the 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.

[0067] [Aromatic hydrocarbon group] Aromatic hydrocarbon groups have 6 or more carbon atoms, usually 36 or fewer, and preferably 24 or fewer. Specific examples include phenyl groups, naphthyl groups, and groups formed by linking multiple phenyl groups.

[0068] [Aromatic heterocyclic groups] Aromatic heterocyclic groups have 3 or more carbon atoms, preferably 4 or more, and usually 36 or fewer, preferably 24 or fewer. Specific examples include thienyl groups and pyridyl groups.

[0069] [Shape of substituent] The substituents may include linear, branched, or cyclic structures.

[0070] [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 4-membered, 5-membered, and 6-membered rings, with specific examples including cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0071] <Alkyl group> Alkyl groups may have substituents, and can 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 or fewer carbon atoms, and even more preferably 10 or fewer carbon atoms. 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 the aforementioned substituent group W 1 It is preferable to select from the following.

[0072] <Aromatic hydrocarbon group> Aromatic hydrocarbon groups refer to monovalent, divalent, or trivalent or more structures of a hydrocarbon aromatic ring structure, depending on the 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 it 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 with 6 members 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, typically 2 to 10 linked groups are used, and 2 to 5 linked groups are 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 aforementioned substituent group W 1 It is preferable to select from the following.

[0073] <Aromatic heterocyclic group> Aromatic heterocyclic groups refer to heteroaromatic ring structures that are monovalent, divalent, or trivalent or more, 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 together, 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 aforementioned substituent group W 1 It is preferable to select from the following.

[0074] <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 within the structure of the compound that is the subject of the explanation 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 together. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, a structure in which 2 to 10 groups are usually shown, and a structure in which 2 to 5 groups are preferred. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0075] <amino group> The amino group may have substituents, preferably a secondary amino group, 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 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, di-n-butylamino 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 the aforementioned substituent group W 1 It is preferable to select from the following.

[0076] <Halogen atom> Halogen atoms are typically fluorine, chlorine, bromine, or iodine atoms. More preferably, they are fluorine atoms.

[0077] <Alkyloxycarbonyl group> The alkyloxycarbonyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 30 carbon atoms, more preferably 20 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 10 carbon atoms or less. 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, and the like. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0078] <Alkyl sulfonyl group> The alkylsulfonyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 1 to 30 carbon atoms, more preferably 20 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 10 carbon atoms 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, and the like. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0079] <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 the 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. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0080] <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 bond to each other to form a ring with the boron atom to which each is bonded. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0081] <Acyl group> The acyl group may have substituents, and the number of carbon atoms is usually not limited, but preferably it has 2 to 50 carbon atoms, more preferably 24 or fewer carbon atoms, and even more preferably 12 or fewer carbon atoms. Specific examples include benzoyl groups and acetyl groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0082] <Aromatic oxy group> Aromatic oxy groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 to 50 carbon atoms, more preferably 30 carbon atoms or less, 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 the aforementioned substituent group W 1 It is preferable to select from the following.

[0083] <Aralkyloxy group> The aralkyloxy 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 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-pentioxyl group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, and 8-phenyl-1-octyloxy group. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0084] <Aromatic thio group> Aromatic thio groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 to 50 carbon atoms, more preferably 30 carbon atoms or less, and even more preferably 20 carbon atoms or less. Specific examples include naphthylthio groups, tolthio groups, and phenylthio groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0085] <Aralkylthio 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, 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, and 8-phenyl-1-octylthio group. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0086] <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 to 50 carbon atoms, more preferably 20 carbon atoms or less, and even more preferably 10 carbon atoms or less. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a group formed by linking multiple such groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0087] <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 part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom. Specifically, the following points can be cited.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] Specific examples of cases where part of the carbon chain is substituted with an aromatic hydrocarbon group include the benzyl group, phenylethyl group, phenylhexyl group, 4-phenylcyclohexylmethyl group, and 4-methylbenzyl group.

[0092] 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.

[0093] Furthermore, a portion of the carbon chain may be 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. Preferably, the group is 2-(tert-butyldimethylsilyloxy)ethyl group, 4-(tert-butyldimethylsilyloxy)butyl group, or 2-(tert-butyldiphenylsilyloxy)ethyl group.

[0094] The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0095] <Heterocyclic group> The heterocyclic 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 20 carbon atoms or less as the upper limit, and even more preferably 10 carbon atoms 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 aforementioned substituent group W 1 It is preferable to select from the following.

[0096] <π-conjugated linking group> A π-conjugated linkage group is a divalent group in the structure of a compound described later, 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 between 2 and 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 vinylene groups, phenylene groups, divalent groups consisting of thiophene rings, furan rings, or pyrrole rings, or groups formed by linking multiple such groups. The substituents that these groups may have are the aforementioned substituent group W 1 It is preferable to select from the following.

[0097] <Nonlinear Optical Materials> In this specification, "nonlinear optical material" refers to a nonlinear optically active compound, a nonlinear optically active polymer compound, or both.

[0098] <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 (1).

[0099] <Explanation of equation (1)> The compound according to the embodiment of the present invention is represented by the following formula (1).

[0100] [ka]

[0101] [In formula (1), Ar 11 Each of these is independently a divalent aromatic group which may have substituents, R 11 and R 13are each independently 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, R 12 and R 14 are each independently a hydrogen atom, a group selected from the following hydrocarbon group group A which may have a substituent, an aromatic group which may have a substituent, an amino group which may have a substituent, a hydroxy group, or a halogen atom, Y 11 are each independently a divalent π-conjugated linking group which may have a substituent, provided that at least one of Y 11 is a vinylene group which may have a substituent, S 11 is a divalent aromatic group which may have a substituent, Z 11 is a group represented by the following formula (2), m 11 are each independently an integer of 0 to 5, m 12 is an integer of 1 to 5, m 13 is an integer of 0 to 5, n 11 is an integer of 1 to 15.]

[0102] (Ar 11 ) Ar 11 are each independently a divalent aromatic group which may have a substituent. The divalent aromatic group which may have a substituent has the same meaning as the description stated in the explanation of the aforementioned phrase. Ar 11 is preferably a divalent group composed of a benzene ring, a naphthalene ring, a 9,9-dialkylfluorene ring, a thiophene ring, or biphenyl, more preferably a divalent group composed of a benzene ring, and these groups may have a substituent.

[0103] (R 11 and R 13 ) R 11 and R 13Each 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, 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 equivalent to the description given in the explanation of the terms above. A divalent aromatic group that may have substituents is defined in the same way as described in the explanation of the terms above.

[0104] From the viewpoint of film formation properties, R 11 and R 13 Preferably, R is a divalent group obtained by removing one hydrogen atom from a group selected from a benzene ring, a naphthalene ring, or hydrocarbon group A which may have substituents with 10 or fewer carbon atoms, and more preferably a divalent group obtained by removing one hydrogen atom from a group selected from a benzene ring, or hydrocarbon group A which may have substituents with 5 or fewer carbon atoms. Also, from the viewpoint of solubility, 11 and R 13 They may be the same or different, but it is preferable that they be different.

[0105] (R 12 and R 14 ) R 12 and R 14 Each of these is independently a hydrogen atom, a group selected from the optionally substituted hydrocarbon group A, an optionally substituted aromatic group, an optionally substituted amino group, a hydroxyl group, or a halogen atom. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "amino group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "halogen atom" is synonymous with the description given in the explanation of the terms above.

[0106] From the perspective of improving nonlinear optical properties, R 12 , R 14The group is preferably a group selected from the hydrocarbon group A which may have substituents, or an amino group which may have substituents; more preferably a group selected from the hydrocarbon group A which has 1 to 20 carbon atoms which may have substituents, or an amino group which may have substituents; and particularly preferably an ethoxy group which may be substituted, or an tertiary amino group which may be substituted.

[0107] (Y 11 ) Y 11 Each is independently a divalent π-conjugated linkage group which may have substituents, where Y 11 At least one of them is a vinylene group which may have substituents. 11 If there are multiple Y 11 The structures may be the same or different. Also, Y 11 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.

[0108] (S 11 ) S 11 This is a divalent aromatic group which may have substituents. A divalent aromatic group which may have substituents is synonymous with the description given in the explanation of the above terms. From the viewpoint of improving nonlinear optical effects, S 11 It is preferably a divalent aromatic group having 3 to 10 carbon atoms, which may have substituents, and a phenylene group, a pyridyl group, or a pyrimidyl group is particularly preferred.

[0109] (Z 11 ) Z 11 This is the base represented by equation (2) described later.

[0110] (substituent) These Ar 11 , R 11 ~R 14 , Y 11 and S 11Unless otherwise specified, the substituent that may be possessed has the same definition as the substituent that each group described in the description of the aforementioned terms may possess.

[0111] (Subscript m 11 , m 12 , m 13 , n 11 ) m 11 each independently represent an integer of 0 to 5, m 12 represents an integer of 1 to 5, m 13 represents an integer of 0 to 5, n 11 represents an integer of 1 to 15.

[0112] From the viewpoint of improving the nonlinear optical properties of the dye, m 11 is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and still more preferably an integer of 0 to 2. From the viewpoint of improving the nonlinear optical properties of the dye, m 12 is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3. From the viewpoint of improving the solubility of the dye, m 13 is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, and still more preferably an integer of 0 to 2. n 11 is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and from the viewpoint of reducing absorption loss, preferably 14 or less, more preferably 13 or less, still more preferably 10 or less, and particularly preferably 5 or less. In one aspect, n 11 can be an integer of 2 to 5.

[0113] (Exemplary structure) Examples of the compound represented by Formula (1) include, but are not limited to, the compounds represented by Formula (1)-1 to Formula (1)-32. In addition, these compounds may further have a substituent.

[0114] [Chemical Formula]

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] <Explanation of equation (2)>

[0123] [ka]

[0124] [In formula (2), *J 21 is, S 11 This is the bonding position with, R 21 and R 22Each 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, and R 21 and R 22 They may be bonded together to form a ring, or R 21 and R 22 R 21 and R 22 These may also form a carbonyl group together with the carbon atom to which they are bonded. R 23 and R 24 Each of these is independently a cyano group, a C2-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents. X 21 is an oxygen atom, a sulfur atom, or NQ 21 And, Q 21 This is a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents.

[0125] (*J 21 ) *J 21 is, S 11 This is the connection point.

[0126] (R 21 and R 22 ) R 21 and R 22 Each of these is independently a group selected from the hydrocarbon group A which may have substituents, or an aromatic group which may have substituents, and R 21 and R 22 They may be bonded together to form a ring, or R 21 and R 22 R 21 and R 22 These may also form a carbonyl group together with the carbon atom to which they are bonded. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above.

[0127] From the perspective of film formation, R 21 and R 22 The group is preferably a group selected from group A of hydrocarbon groups having 1 to 20 carbon atoms, which may have substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may be substituted. Methyl groups, ethyl groups, linear or branched propyl groups, phenyl groups, and naphthyl groups are particularly preferred, with methyl groups and phenyl groups being the most preferred. These R 21 and R 22 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.

[0128] (R 23 and R 24 ) R 23 and R 24 Each of these is independently a cyano group, a C2-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents. A C2-C30 alkyloxycarbonyl group, which may have substituents, is synonymous with the description given in the explanation of the terms above. A C1-C30 alkylsulfonyl group, which may have substituents, is defined in the same way as described in the explanation of the terms above.

[0129] From the perspective of improving nonlinear optical properties, R 23 and R 24 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.

[0130] (X 21 ) X 21 is an oxygen atom, a sulfur atom, or NQ 21 That is the case.

[0131] (Q 21 ) Q 21 This is a hydrogen atom, a group selected from the optionally substituted hydrocarbon group A, or an optionally substituted aralkyl group. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aralkyl group which may have substituents" is synonymous with the description given in the explanation of the terms above.

[0132] From the viewpoint of film formation, a group selected from the hydrocarbon group A having 1 to 20 carbon atoms, 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.

[0133] (substituent) These R 21 ~R 24 and Q 21 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] (Example structure) Examples of structures represented by formula (2) include, but are not limited to, those represented by formulas (2)-1 to (2)-35. Furthermore, these compounds may have substituents.

[0135] [ka]

[0136] [ka]

[0137] <Preferred form of formula (1) 1> Y in equation (1) above 11 At least one of them is expressed independently by equation (3), where n in equation (1) 11 If it is 2 or more, then R in equation (3) below 31 and R 32 is, other Y 11 R included 31 or R 32 It is preferable that they are connected to form a ring. When they are connected to form a ring, R 31 and R 32 Either of them may be a single bond.

[0138] <Explanation of equation (3)>

[0139] [ka]

[0140] [In formula (3), R 31 and R 32 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 31 and R 32 They may be joined together to form a ring.

[0141] (R 31 and R 32 ) R 31 and R 32 Each of these is independently a hydrogen atom, a group selected from optionally substituted hydrocarbon group A, an optionally substituted aromatic group, a hydroxyl group, an optionally substituted amino group, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "amino group which may have substituents" is synonymous with the description given in the explanation of the terms above. The term "halogen atom" is synonymous with the description given in the explanation of the terms above. A boryl group that may have substituents is defined in the same way as described in the explanation of the terms above. Also, R 31 and R 32 They may be bonded together to form a ring. 31 and R 32 When R is bonded to form a ring, 31 and R 32 Either of them may be a single bond. R 31 and R 32 The relationship can be either cis-form or trans-form.

[0142] (substituent) These R 31 and R 32 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.

[0143] <Preferred form of formula (1) 2> Y in equation (1) above 11 However, each can be expressed independently by the following equations (4), (5), or (6), Y 11 At least one of them is expressed by the following equation (4), where n in equation (1) is 11 If it is 2 or more, Y 11 R inside 41 , R 42 , R 51 , R 52 , and R 61 ~R 67 is, other Y 11 R included 41 , R 42 , R 51 , R 52 , or R 61 ~R67 It is preferable that they are connected to form a ring. When they are connected to form a ring, R 41 , R 42 , R 51 , R 52 and R 61 ~R 67 Either of them may be a single bond.

[0144] <Explanation of equation (4)>

[0145] [ka]

[0146] [In formula (4), R 41 and R 42 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 41 and R 42 They may be joined together to form a ring.

[0147] (R 41 and R 42 ) R 41 and R 42 R in equation (3) 31 and R 32 It is synonymous with [the above].

[0148] From the viewpoint of improving the nonlinear optical effect, preferably, R 41 , R 42 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.

[0149] <Explanation of equation (5)>

[0150] [ka]

[0151] [In formula (5), R 51 and R 52 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 51 and R 52 They may be bonded together to form a ring. X 51 is an oxygen atom, a sulfur atom, or NQ 51 And, Q 51 This is 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 which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, or a boryl group which may have substituents.

[0152] (R 51 and R 52 ) R 51 and R 52 R in equation (3) 31 and R 32 It is synonymous with [the above].

[0153] From the viewpoint of improving the nonlinear optical effect, preferably, R 51 , 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 most preferably a hydrogen atom.

[0154] (X 51 ) X 51 is an oxygen atom, a sulfur atom, or NQ 51 That is the case.

[0155] From the viewpoint of improving nonlinear optical effects, sulfur atoms are preferred.

[0156] (Q 51 ) Q 51 This is a hydrogen atom, a group selected from optionally substituted hydrocarbon groups A, an optionally substituted aromatic group, a hydroxyl group, an optionally substituted amino group, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group. The groups selected from group A of hydrocarbon groups that may have substituents are equivalent to those described in the explanation of the terms above. The term "aromatic group which may have substituents" is synonymous with the description given in the explanation of the terms above.

[0157] From the viewpoint of film formation, groups selected from hydrocarbon groups A having 1 to 20 carbon atoms, which may have substituents, and aromatic hydrocarbon groups having 6 to 60 carbon atoms are preferred; groups selected from hydrocarbon groups A having 1 to 20 carbon atoms, which may have substituents, and aromatic hydrocarbon groups having 6 to 30 carbon atoms are more preferred; and groups selected from hydrocarbon groups A having 1 to 10 carbon atoms, which may have substituents, and aromatic hydrocarbon groups having 6 to 20 carbon atoms are particularly preferred.

[0158] (substituent) Q 51 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.

[0159] <Explanation of equation (6)>

[0160] [ka]

[0161] [In formula (6), R 61 ~R 67Each 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R 61 ~R 67 At least two of them may be joined together to form a ring.

[0162] (R 61 ~R 67 ) R 61 ~R 67 R in equation (3) 31 and R 32 This is synonymous with R. 61 ~R 67 In the case of R 61 ~R 67 At least two of them may be joined together to form a ring.

[0163] From the viewpoint of improving the nonlinear optical effect, preferably, R 61 R is a hydrogen atom, a group selected from the optionally substituted hydrocarbon group A, or an optionally substituted aromatic group, 62 ~R 67 is a group selected from the hydrocarbon group A, which may have a hydrogen atom or substituents. More preferably, R 61 R is a hydrogen atom or a group selected from hydrocarbon group A which may have substituents, 62 , R 63 , R 66 , R 67 R is a hydrogen atom, 64 , R 65 is a hydrogen atom, or a group selected from hydrocarbon group A which may have substituents. Most preferably, R 71 R is a hydrogen atom or a group selected from hydrocarbon group A which may have substituents, 62 , R 63 , R 66 , R 67 R is a hydrogen atom, 64 , R 65is a hydrogen atom or an alkyl group.

[0164] (substituent) These R 61 ~R 67 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.

[0165] <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 a nonlinear optically active polymer compound includes a polymer compound (hereinafter also referred to as "the polymer compound") that contains a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) as at least one selected from the substituent and the main chain. The polymer compound according to the embodiment of the present invention contains a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) as at least one selected from the substituent and the main chain.

[0166] From the viewpoint of reactivity when introduced as substituents and / or main chains into polymer compounds, a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is R 14 , R 51 , R 52 or R 61 It is preferable that the group is one from which a hydrogen atom has been removed, R 14 or R 61 It is more preferable that the group is one from which a hydrogen atom has been removed, R 14 It is even more preferable that the group is one from which a hydrogen atom has been removed.

[0167] In this specification, the group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is also referred to as the "pigment group."

[0168] In this polymer compound, the pigment group may be present as part of the main chain of the repeating unit in the polymer compound, or it may be bonded as part of the side chain.

[0169] <Polymer compounds> The polymer compounds containing the aforementioned dye group as part of the main chain or side chain of the repeating unit are not particularly limited, but specific examples include poly(meth)acrylic acid esters (e.g., polymethyl methacrylate (PMMA), polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly DCPMA)). Examples include AdMA, poly(DCPMA-co-MMA), poly(AdMA-co-MMA), polycarbonylaminoethyl methacrylate, etc., polyamide, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, maleimide-norbornene copolymer, polynorbornene, 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, fluoropolymer, and copolymers thereof. (Meth)acrylic means at least one selected from the group consisting of acrylic and methacrylic. The same applies to (meth)acrylate, etc.

[0170] In particular, from the viewpoint of being generally excellent as an optical material, it is more preferable to be at least one selected from the group consisting of poly(meth)acrylic acid ester, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, maleimide-norbornene copolymer, polynorbornene, and copolymers thereof. From the viewpoint of compound stability, polystyrene, polymethacrylic acid ester, and maleimide-styrene copolymer are most preferred. Preferred examples of polymethacrylates include polyadamantyl methacrylate (poly AdMA), polyalkyloxycarbonylaminoethyl methacrylate, polymethyl methacrylate (PMMA), and poly(cyclic or linear) alkyl methacrylates.

[0171] <Preferred range of the content of repeating units containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1), relative to the total amount of each repeating unit of this polymer compound> In the polymer compound according to the embodiment of the present invention, i.e., the polymer compound, when expressing the content of repeating units containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) as a mole percentage, there are no particular restrictions on the mole percentage of the dye group relative to the total of each repeating unit of the polymer compound. 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.

[0172] In the polymer compound according to the embodiment of the present invention, i.e., the polymer compound, when the content of repeating units containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is expressed as a mass percentage, there are no particular restrictions on the molar percentage of the dye group relative to the total of each repeating unit of the polymer compound. However, from the viewpoint of balancing electro-optic effect and solubility, it is preferably 10% by mass or more as a lower limit, more preferably 15% by mass or more, and even more preferably 20% by mass or more, and it is preferably 90% by mass or less as an upper limit, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.

[0173] The content of this pigment group in this polymer compound is: 1It is calculated by methods such as H-NMR, absorbance measurement, and gel permeation chromatography (GPC), but preferably, 1 H-NMR, absorbance measurement, most preferably 1 It is calculated by 1H-NMR. 1 A specific method for calculating the content of the pigment group in this polymer compound using 1H-NMR is as follows: The spectral integral value originating from a specific hydrogen in the compound, represented by formula (1), is used as a reference. By taking the ratio of this value to the spectral integral value originating from a specific hydrogen in each repeating unit of the polymer compound, the molar ratio of the pigment group to each repeating unit of the polymer compound can be calculated. From this molar ratio, the apparent mass ratio can be calculated, and the content of the pigment group in this polymer compound can be determined.

[0174] The specific method for calculating the content of the pigment group in this polymer compound by absorbance measurement is as follows: the absorbance is calculated by dividing the maximum absorbance obtained when measuring the absorbance of a solution in which the compound represented by formula (1) is dissolved at a predetermined concentration by the concentration, and then calculating the ratio of the absorbance obtained when the polymer compound is similarly measured for absorbance. The absorbance is measured using an ultraviolet-visible-near-infrared spectrophotometer.

[0175] <Preferred range of molecular weight for this polymer compound> The weight-average molecular weight of this polymer compound is not particularly limited, but it 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 this polymer compound is determined by measuring the weight-average molecular weight of polystyrene as a standard using GPC.

[0176] There are no particular restrictions on the molecular weight distribution of this polymer compound, 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 this polymer compound is 3 or less. The molecular weight distribution of this polymer compound is confirmed by measuring the ratio of the number-average molecular weight to the weight-average molecular weight using polystyrene as a standard, via GPC (Gross Propagation).

[0177] <Preferred range of thermophysical properties (Tg and Td) of this polymer compound> There are no particular restrictions on the glass transition temperature (Tg) of this polymer compound, but it is generally between 40°C and 300°C. A Tg 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 poling process, a Tg 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 this polymer compound is determined 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).

[0178] There are no particular restrictions on the decomposition temperature (Td) of this polymer compound, 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 this polymer compound is determined by measuring the temperature at which the mass decreases by 5% using a thermogravimetric differential thermal analyzer (TG-DTA).

[0179] <-W 51 -X 51 -Explanation> The group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is -W 51 -X 51 - may be included in the polymer compound as at least one selected from the substituent and the main chain via -W. 51 -X 51 - If present, W 51 or X 51 Either of these bonds with the element from which the hydrogen atom in equation (1) has been removed.

[0180] (W 51 ) W 51represents a single bond, a carbonyl group, a thionyl group, a phenyl group, or a triazole group.

[0181] (X 51 ) X 51 represents a single bond, an oxygen atom, a sulfur atom, a phenyl group, or an -NH- group.

[0182] (Example structure) -W 51 -X 51 Examples of structures represented by - include, but are not limited to, those represented by formulas (WX)-1 to (WX)-12. In formulas (WX)-1 to (WX)-12, * indicates a group obtained by removing at least one hydrogen atom from the compound represented by formula (1), and the bonding position with the repeating structure of the polymer compound.

[0183] [ka]

[0184] <Specific examples of repeating units containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1)> The following are specific examples of repeating units included in the polymer compounds according to embodiments of the present invention, which include a group obtained by removing at least one hydrogen atom from the compound represented by formula (1). The present invention is not limited to these examples.

[0185] [ka]

[0186] [ka]

[0187] [ka]

[0188] [ka]

[0189] <Repeating units that may be included> The polymer compound according to the embodiment of the present invention may contain repeating units (R) in addition to repeating units containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1). Here, the repeating units (R) do not include repeating units containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1). The durability of the polymer compound is improved by including a repeating unit different from the repeating unit that contains a group obtained by removing at least one hydrogen atom from the compound represented by formula (1).

[0190] 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.), polyamides, polyimides, polycarbonates, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyesters, polyolefins, polyphenylene sulfide, aromatic polyamines, polyamines, polyureas, silicone resins, epoxy resins, polyvinyl chloride, and repeating units that constitute fluoropolymers. 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.

[0191] The following are specific examples of repeating units (R) that may be included in the polymer compound according to the embodiment of the present invention. The repeating units (R) are not limited to these.

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] <Bridging group> The polymer compound according to the embodiment of the present invention may have crosslinking groups. Having crosslinking groups 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 lon 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.

[0196] The polymer compounds according to the embodiments of the present invention 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.

[0197] <Example of a repeating unit containing a crosslinking group> The following are preferred examples of repeating units (CLs) containing crosslinking groups. The present invention is not limited to these examples.

[0198] [ka]

[0199] <Preferred specific examples of polymer compounds containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1)> The following are some preferred examples. The present invention is not limited to these. PA represents a repeating unit (Pa) comprising a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) above, and PC represents the repeating unit (R) above, or a repeating unit (CL) comprising a bridging group.

[0200] [Table 1-1]

[0201] [Table 1-2]

[0202] [Table 1-3]

[0203] [Table 1-4]

[0204] [Table 1-5]

[0205] [Table 1-6]

[0206] [Table 1-7]

[0207] [Table 1-8]

[0208] [Table 1-9]

[0209] [Table 1-10]

[0210] [Table 1-11]

[0211] <Composition> A composition according to an embodiment of the present invention is a composition comprising a compound represented by formula (1) and a polymer material, or a composition comprising the polymer compound comprising a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) as at least one selected from substituents and main chain, or a composition comprising a compound represented by formula (1) and the polymer compound. These compositions may further contain a solvent. The components of the composition according to the embodiment of the present invention include the compound represented by formula (1) above, the polymer compound containing a group obtained by removing at least one hydrogen atom from the compound represented by formula (1) as at least one selected from substituents and main chains, and the polymer material, each of which may be included independently as only one type or as two or more types.

[0212] [Solid content] Solid content refers to the amount of components other than the solvent contained in the composition. Even if a component other than the solvent is liquid at room temperature, it is not included in the solvent and is instead included in the solid content. There are no particular restrictions on the content of the nonlinear optical material in the composition, but it is preferable to have a higher content of the component exhibiting nonlinear optical activity. For example, it is preferable to have 1 to 100 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 10 to 100 parts by mass per 100 parts by mass of solid content.

[0213] [Polymer materials] When the nonlinear optical material is a nonlinear optically active compound, polymer materials can be used in the composition.

[0214] As for the polymer material, there are no particular restrictions as long as it can disperse the nonlinear optically active compound, but transparent polymers that do not scatter are preferred for use as optical materials. 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, and the like. Of these, from the viewpoint of molecular orientation, at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, and copolymers thereof is preferred, and at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, and polycarbonate is more preferred. 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.

[0215] There are no particular restrictions on the content of polymer material in the composition, but from the viewpoint of coatability, it is preferably 0 to 99 parts by mass, more preferably 0 to 95 parts by mass, and even more preferably 0 to 90 parts by mass per 100 parts by mass of solid content.

[0216] [solvent] The solvents that can be used in the compositions according to the embodiments of the present invention are not particularly limited as long as they dissolve the nonlinear optically active compound and polymer material, or the nonlinear optically active polymer compound, but are preferably organic solvents, for example aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and styrene; aliphatic hydrocarbons such as n-hexane and n-heptane; chlorobenzene, orthodichlorobenzene, chloroform, dichloromethane, dibromomethane, 1,2-dichloroethane, trifluoromethylbenzene, and 3-methoxyben. Halogenated hydrocarbons such as benzotrifluoride and 3-methoxybenzotrifluoride; ketones such as acetone, ethyl methyl ketone, isopropyl methyl ketone, isobutyl methyl ketone, butyl methyl ketone, diacetone alcohol, diethyl ketone, cyclopentanone, and cyclohexanone; ethyl acetate, propyl acetate, phenyl acetate, 2-methoxyethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethyl lactate, γ-butyrolactone, ethyl benzoate, methyl benzoate, benzoyl benzoate, 2-ethylhexyl benzoate, 4-methyl Esters such as ethyl benzoate; 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 alcohol, pentanol, 2-methylbutanol, 2-methyl-2-butanol, cyclohexanol, 2-methylpentanol, octanol, 2-ethylhexanol, benzyl alcohol, furfuryl alcohol, tert-butyl alcohol Alcohols such as trahydrofurfuryl alcohol; glycols such as ethylene glycol, propylene glycol, hexylene glycol, trimethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol; 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;Examples include 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.

[0217] Of the above 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 coating properties, 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.

[0218] There are no particular restrictions on the solvent content in the composition, but from the viewpoint of film uniformity, it is preferably 80 to 99 parts by mass per 100 parts by mass of the composition, more preferably 85 to 99 parts by mass, and even more preferably 85 to 98 parts by mass, from the viewpoint of ensuring the stability of the composition.

[0219] [Other ingredients] The composition may include nonlinear optical materials, polymer materials, solvents, and other components. Other components are not particularly limited as long as they do not hinder the purpose for which the composition is used, but may, as necessary, 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, etc., as long as they do not impair the effects of the present invention.

[0220] There are no particular restrictions on the content of other components in the composition, but from the viewpoint of film uniformity, it is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 1 part by mass per 100 parts by mass of the composition.

[0221] [Method for producing the composition] There are no particular limitations on the method for producing the composition, as long as it includes the step of dissolving the above-mentioned nonlinear optical material in the above-mentioned solvent. One embodiment of the method for producing the composition includes the steps of mixing and heating and stirring the above-mentioned polymer material and the above-mentioned solvent to dissolve it, mixing and stirring the above-mentioned nonlinear optically active compound with this solution to dissolve it, and filtering the solution. Another embodiment of the method for producing the composition includes the steps of mixing and stirring the above-mentioned nonlinear optically active polymer compound with the above-mentioned solvent to dissolve it, and filtering the solution.

[0222] [Uses of the composition] There are no particular restrictions on the use of the composition, but it is commonly used to create nonlinear optical materials in the form of films or thin films. Nonlinear optical materials, in the form of films or thin films, can be used in nonlinear optical elements. That is, the composition can be used as an ink for forming nonlinear optical elements.

[0223] There are no particular restrictions on the method for creating a film or thin film from a composition, but known methods such as injection molding, press molding, soft lithography, and wet coating can be used. Of these, wet coating methods such as spin coating, blade coating, immersion coating, and inkjet coating can be cited from the viewpoint of simplicity of manufacturing equipment, mass production capability, and film quality (uniformity of film thickness, low number of defects such as bubbles, etc.).

[0224] One embodiment involves coating a substrate with a composition obtained by dissolving the above-mentioned nonlinear optically active compound and the above-mentioned polymer material in the above-mentioned solvent, and then drying it. Drying here refers to a process of drying by, for example, placing the substrate on a heating device such as a hot plate and heating it, or a process of drying by placing the coated substrate in a chamber and creating a vacuum, or a process that combines both. Another embodiment involves coating a substrate with a composition obtained by dissolving the above-mentioned nonlinear optically active polymer compound in the above-mentioned solvent, and then heating and vacuum drying it.

[0225] <Nonlinear Optical Elements> The nonlinear optical element according to the embodiment of the present invention is made using the nonlinear optical material described above. That is, the nonlinear optical element according to the embodiment of the present invention is either a nonlinear optical element containing a compound according to the embodiment of the present invention, or a nonlinear optical element containing a polymer compound according to the embodiment of the present invention. For example, a nonlinear optical element according to an embodiment of the present invention can be made using the above-described composition.

[0226] The nonlinear optical element is not particularly limited as long as it uses the nonlinear optical material described above and operates based on nonlinear optical effects, but examples include wavelength conversion elements, photorefractive elements, and electro-optic elements. Of these, nonlinear optical elements that operate based on electro-optic effects 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.

[0227] As an electro-optic element, it is preferable to use an element having a structure in which a film containing a nonlinear optical material is formed on a substrate and sandwiched between electrode pairs for input electrical signals.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] The electro-optic element is preferably formed to include a waveguide structure, and it is particularly preferable to incorporate the above-mentioned nonlinear optical material into the core layer of the waveguide.

[0232] A cladding layer (hereinafter also referred to as the "lower cladding layer" in this specification) may be formed between the core layer containing the aforementioned nonlinear optical material 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; polyimide; and glass.

[0233] After forming the core layer with the nonlinear optical material described above, 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.

[0234] 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.

[0235] 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.

[0236] When forming channel-type waveguides or ridge-type waveguides as described above, known device structures such as linear, Y-branch, directional coupler, and Mach-Zehnder 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. An example of application to optical information communication devices is application to an optical modulator equipped with the nonlinear optical elements described above, preferably an optical modulator equipped with nonlinear optical elements that operate based on the electro-optic effect described above. [Examples]

[0237] 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.

[0238] [ 1 [Measurement of H-NMR] Nuclear magnetic resonance spectrum ( 1 ¹H-NMR was measured using a JEOL Ltd. JNM-ECZ400S, with CDCl3 as the solvent, and the chemical shift value δ from the internal standard tetramethylsilane is expressed in ppm. The symbols used have the following meanings. s: singlet, d: doublet, dd: double doublet, t: triplet, m: multiplet

[0239] <Synthesis of dyes and EO polymers> Dyes 1-7 and EO polymer 1 were synthesized using the following method.

[0240] <Synthesis of Compound 1> Compound 1, described below, was synthesized using the same method as compound 10b, as described in Journal of Polymer Science Part A: Polymer Chemistry, 2010, 49, 47-54.

[0241] [ka]

[0242] <Synthesis of Compound 2>

[0243] [ka]

[0244] Under a nitrogen stream, 4-bromosalicylicaldehyde (20.1 g, 0.10 mol), potassium carbonate (27.6 g, 0.20 mol), and DMF (200 mL) were added to a 500 mL three-necked flask and stirred. After cooling to 0°C in an ice bath, benzyl bromide (20.5 g, 0.12 mol) was added dropwise, and the mixture was stirred at 0°C for 2 hours. After the reaction, the mixture was heated to room temperature, the reaction solution was poured into water (400 mL), and extracted with ethyl acetate (400 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 2 (7.60 g, yield 77.6%).

[0245] <Synthesis of Compound 3>

[0246] [ka]

[0247] Under a nitrogen atmosphere, compound 2 (16.3 g, 56.1 mmol), diethyl-2-thienylmethylphosphonate (15.8 g, 67.3 mmol), and THF (163 mL) were mixed in a 500 mL three-necked flask and cooled to 0°C in an ice bath. Potassium tert-butoxide (6.92 g, 61.7 mmol) was slowly added to the reaction solution, and the mixture was heated to room temperature and stirred for 4 hours. After the reaction, the reaction solution was poured into water (100 mL) and extracted with ethyl acetate (400 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 3 (17.4 g, yield 83.7%).

[0248] <Synthesis of Compound 4>

[0249] [ka]

[0250] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 3 (17.0 g, 45.8 mmol) and 2,4,6-trimethylaniline (9.30 g, 68.7 mmol) in toluene (229 mL) was added. Sodium tert-butoxide (11.0 g, 114.5 mmol), palladium acetate (103 mg, 0.46 mmol), and 2,2'-bis(diphenylphosphin-1-1')-binaphthyl (BINAP) (570 mg, 0.92 mmol) were then added, and the mixture was stirred at 100 °C for 10 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 4 (13.7 g, yield 70.3%).

[0251] <Synthesis of Compound 5>

[0252] [ka]

[0253] In a 1 L flask, 2-(N-methylanilino)ethanol (80.0 g, 0.53 mol), pyridine (400 mL), and 1,4-dioxane (400 mL) were mixed and cooled to 0°C. Iodine (201 g, 0.80 mol) was then added. The reaction solution was then heated to 35°C and stirred for 7 hours. After the reaction was complete, the reaction solution was diluted with dichloromethane (800 mL) and washed with saturated sodium thiosulfate aqueous solution. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 5 (74.0 g, yield 50.4%).

[0254] <Synthesis of Compound 6>

[0255] [ka]

[0256] Under a nitrogen atmosphere, a solution of compound 5 (20.0 g, 72.2 mmol) in DMF (200 mL) was cooled to 0°C in a 500 mL flask, and then tert-butyldimethylchlorosilane (TBDMSCl) (11.90 g, 79.4 mmol) was added. The reaction solution was then heated to 25°C and stirred for 2 hours. After the reaction, the reaction solution was poured into water (200 mL) and extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 6 (22.9 g, yield 81.1%).

[0257] <Synthesis of Compound 7>

[0258] [ka]

[0259] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 4 (11.9 g, 28.0 mmol) and compound 6 (13.1 g, 33.6 mmol) in toluene (186 mL) was added to sodium tert-butoxide (6.72 g, 69.9 mmol), Pd2(dba)3 (512 mg, 0.56 mmol), and tert-Bu3PHBF4 (649 mg, 2.24 mmol). The mixture was then stirred at 100 °C for 6.5 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 7 (12.1 g, yield 62.9%).

[0260] <Synthesis of Compound 8>

[0261] [ka]

[0262] Under a nitrogen stream, a solution of compound 7 (12.0 g, 17.4 mmol) in THF (120 mL) was cooled to -78°C in a 500 mL three-necked flask, and n-BuLi (1.6 M in hexane, 12 mL) was added. After stirring at -78°C for 1 hour, DMF (5.4 mL) diluted with THF (5.0 mL) was added, and the mixture was heated to 0°C and stirred for 3 hours. After the reaction, water (50 mL) was added to the reaction solution, and it was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 8 (9.09 g, yield 72.8%).

[0263] <Synthesis of Compound 9>

[0264] [ka]

[0265] Under a nitrogen stream, potassium hydroxide (17.8 g, 0.28 mol) was slowly added to a DMSO (540 mL) solution of dihexylamine (25.0 g, 0.14 mol) in a 500 mL three-necked flask. The mixture was stirred at room temperature for 30 minutes, and then 1-bromo-3,5-dimethylbenzene (50.0 g, 0.28 mol) was added dropwise. After the addition was complete, the temperature was raised to 50°C and the mixture was stirred for 9 hours. After the reaction, the reaction solution was poured into water (500 mL) and extracted with ethyl acetate (800 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 9 (25.2 g, yield 64.4%).

[0266] <Synthesis of Compound 10>

[0267] [ka]

[0268] Under a nitrogen atmosphere, compound 9 (22.2 g, 76.7 mmol) and 4 M aqueous hydrogen chloride solution (114 mL) were mixed in a 500 mL three-necked flask. After cooling to -5°C, sodium nitrite solution (5.82 g, 84.4 mmol) aqueous solution (3 mL) was added dropwise while stirring. After addition, the mixture was stirred at -5°C to 0°C for 1 hour. Then, 8 M aqueous hydrogen chloride solution (205 mL) was added to the reaction solution, and zinc powder (22.1 g, 337 mmol) was slowly added at 0°C. The reaction solution was heated to 25°C and stirred for 4 hours. After stirring, it was neutralized with sodium hydroxide and extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 10 (15.1 g, yield 64.5%).

[0269] <Synthesis of Compound 11>

[0270] [ka]

[0271] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 3 (19.3 g, 51.9 mmol) and compound 10 (15.8 g, 51.9 mmol) in toluene (259 mL) was prepared. Sodium tert-butoxide (12.5 g, 130 mmol), palladium acetate (116 mg, 0.52 mmol), and 2,2'-bis(diphenylphosphin-1-1')-binaphthyl (BINAP) (646 mg, 1.04 mmol) were added, and the mixture was stirred at 100 °C for 6 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 11 (24.0 g, yield 73.1%).

[0272] <Synthesis of Compound 12>

[0273] [ka]

[0274] Under a nitrogen atmosphere, in a 100 mL three-necked flask, a solution of compound 11 (595 mg, 1.0 mmol) and compound 6 (470 mg, 1.2 mmol) in toluene (6.70 mL) was added. Sodium tert-butoxide (240 g, 2.5 mmol), Pd2(dba)3 (18.0 mg, 0.02 mmol), and tert-Bu3PHBF4 (23 mg, 0.039 mmol) were then added, and the mixture was stirred at 100 °C for 8 hours. After the reaction, water (10 mL) was added to the reaction solution, and it was extracted with ethyl acetate (20 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 12 (586 mg, yield 63.6%).

[0275] <Synthesis of Compound 13>

[0276] [ka]

[0277] Under a nitrogen stream, a solution of compound 12 (2.10 g, 2.4 mmol) in THF (21 mL) in a 100 mL three-necked flask was cooled to -78 °C, and n-BuLi (1.6 M in hexane, 1.70 mL) was added. After stirring at -78 °C for 1 hour, DMF (0.74 mL) diluted with THF (0.8 mL) was added, and the temperature was raised to 0 °C and stirred for 3 hours. After the reaction, water (50 mL) was added to the reaction solution and extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 13 (1.56 g, yield 73.1%).

[0278] <Synthesis of Compound 14>

[0279] [ka]

[0280] Under a nitrogen stream, triethylamine (55.9 mL, 0.40 mol) was added to a solution of 4-bromobenzyl alcohol (50.0 g, 0.27 mol) in DMF (835 mL) in a 2 L flask, and the reaction solution was cooled to 0°C. While stirring, tert-butylchlorodiphenylsilane (83.0 g, 0.30 mol) was added dropwise to the reaction solution, and the temperature was raised to room temperature, after which stirring was continued for 4 hours. After the reaction, water (1.0 L) was added to the reaction solution, and it was extracted with ethyl acetate (2.0 L). The organic layer was washed with water (250 mL x 2), dried over magnesium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 14 (100.9 g, yield 88.7%).

[0281] <Synthesis of Compound 15>

[0282] [ka]

[0283] Under a nitrogen atmosphere, a solution of acetone cyanohydrin (19.4 g, 0.23 mol) in pyridine (18.1 mL) was cooled to -10°C in a 200 mL three-necked flask, and chlorotrimethylsilane (25.0 mL, 0.20 mol) was added while stirring. After stirring at -10°C for 20 minutes, the temperature was raised to room temperature and stirred for a further 14 hours. After the reaction, water (100 mL) was added to the reaction solution and extracted with ethyl acetate (200 mL). The organic layer was washed with water (100 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. Compound 15 (22.1 g, yield 71.1%) was obtained by vacuum distillation of the resulting crude product.

[0284] <Synthesis of Compound 16>

[0285] [ka]

[0286] Under a nitrogen stream, a solution of compound 14 (44.5 g, 104.5 mmol) in THF (615 mL) was cooled to -72°C in a 2 L three-necked flask, and n-BuLi hexane solution (1.6 mol / L, 71.8 mL, 115 mmol) was added dropwise over 25 minutes. After the addition was complete, the mixture was stirred at -72°C for 40 minutes. Then, at -72°C, a solution of compound 15 (19.7 g, 125.4 mmol) in THF (197 mL) was added dropwise to the reaction solution over 15 minutes. After addition, the mixture was stirred at 0°C for 1.5 hours, and then stirred at room temperature for 2 hours. Then, aqueous hydrogen chloride solution (2.0 mol / L, 261 mL) was added at room temperature, and the mixture was stirred for 30 minutes. The product was extracted with ethyl acetate (1000 mL), the organic layer was washed with water (250 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel chromatography to obtain compound 16 (31.8 g, yield 70.1%).

[0287] <Synthesis of Compound 17>

[0288] [ka]

[0289] Under a nitrogen atmosphere, compound 16 (18.0 g, 41.6 mmol) and malononitrile (8.25 g, 125 mmol) were dissolved in anhydrous pyridine (90 mL) in a 300 mL three-necked flask. Molecular sieves 3A (18 g) were added to the solution, followed by the addition of acetic acid (150 mg, 2.5 mmol), and the mixture was stirred at room temperature for 96 hours. After removing the molecular sieves by filtration, the filtrate was flushed with water (500 mL), and the resulting precipitate was collected by filtration. The filtered material was washed with water and dried. The resulting crude compound was purified by silica gel column chromatography to obtain compound 17 (9.6 g, yield 43.6%).

[0290] <Synthesis of Compound 18>

[0291] [ka]

[0292] Under a nitrogen atmosphere, compound 17 (20.0 g, 37.8 mmol) was dissolved in anhydrous THF (160 mL) in a 300 mL three-necked flask and stirred at room temperature. To the solution, a THF solution of tetra-n-butylammonium fluoride (TBAF) (1 mol / L, 56.6 mL, 56.6 mmol) was added and stirred at room temperature for 24 hours. After the reaction, water (100 mL) was added to the reaction solution and extracted with dichloromethane (100 mL x 3). The organic layer was washed with water (100 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 18 (6.2 g, yield 56.4%).

[0293] <Synthesis of Compound 19>

[0294] [ka]

[0295] Under a nitrogen atmosphere, compound 18 (6.2 g, 21.3 mmol) was dissolved in anhydrous dichloromethane (50 mL) in a 200 mL three-necked flask and stirred at room temperature. Thionyl chloride (5.06 g, 42.6 mmol) was added to the solution and stirred at room temperature for 24 hours. The organic layer was washed with water (50 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 19 (4.0 g, yield 60.7%).

[0296] <Synthesis of Compound 20>

[0297] [ka]

[0298] Under a nitrogen atmosphere, compound 19 (4.0 g, 12.9 mmol) and triphenylphosphine (16.9 g, 64.6 mmol) were dissolved in anhydrous toluene (40 mL) in a 200 mL three-necked flask and stirred for 8 hours while heating to reflux temperature. After the reaction, the resulting white solid was collected by filtration, washed with toluene (50 mL), and dried under reduced pressure to obtain compound 20 (5.8 g, yield 78.5%).

[0299] The results of the NMR measurement of compound 20 are shown below. 1 H-NMR(400MHz,CDCl3)δ7.77-7.82(m,9H),7.68-7.63(m,6H),7.49(dd,2H),7.41(dd,2H),5.82(d,2H),1.70(s,6H)

[0300] <Synthesis of pigment 1>

[0301] [ka]

[0302] Under a nitrogen stream, compound 20 (1.50 g, 2.62 mmol) was dissolved in anhydrous THF (10 mL) in a 30 mL Schlenk flask. The solution was then cooled to -78°C, and n-BuLi hexane solution (1.6 mol / L, 1.47 mL, 2.36 mmol) was added dropwise. After the addition was complete, the mixture was stirred at -78°C for 15 minutes, and compound 1 (1.33 g, 2.62 mmol) was added. After the addition, the mixture was raised to room temperature and stirred for 30 minutes. Further stirring was carried out at reflux temperature for 24 hours. After the reaction, methanol (1.5 mL) was added, and the reaction solution was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain dye 1 (300 mg, yield 15.0%).

[0303] The results of the NMR measurement of dye 1 are shown below. 1H-NMR(400MHz,CDCl3)δ7.88(d,2H),7.60(d,2H),7.30-7.51(m,8H),7.11(d,1H),7.04(d,1H),6.84(d,1H),6.81(d,1H) ),6.33(dd,1H),6.23(d,1H),5.17(s,2H),3.73(t,2H),3.47(t,2H),3.01(s,3H),1.85(s,6H),0.88(s,9H),0.01(s,6H)

[0304] <Synthesis of pigment 2>

[0305] [ka]

[0306] Under a nitrogen stream, compound 20 (600 mg, 1.05 mmol) was dissolved in anhydrous THF (10 mL) in a 30 mL Schlenk flask. The solution was then cooled to -78°C, and n-BuLi hexane solution (1.6 mol / L, 0.59 mL, 0.94 mmol) was added dropwise. After the addition was complete, the mixture was stirred at -78°C for 15 minutes, and compound 8 (753 mg, 1.05 mmol) was added. After the addition, the mixture was raised to room temperature and stirred for 30 minutes. Further stirring was carried out at reflux temperature for 24 hours. After the reaction, methanol (0.6 mL) was added, and the reaction solution was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain dye 2 (210 mg, yield 20.5%).

[0307] The results of the NMR measurement of dye 2 are shown below. 1H-NMR(400MHz,CDCl3)δ7.89(d,2H),7.61(d,2H),7.22-7.41(m,12H),7.05(d ,1H),6.81-6.90(m,5H),6.57(s,1H),6.36(s,1H),4.97(s,2H),3.77(t,2H), 3.77(t,2H),6.23(d,1H),5.17(s,2H),3.77(t,2H),3.45(s,2H),2.96(s,2H) ,2.34(s,3H),1.96(s,6H),1.86(s,6H),1.55(s,4H),0.88(s,9H),0.04(s,6H)

[0308] <Synthesis of pigment 3>

[0309] [ka]

[0310] Under a nitrogen stream, compound 20 (600 mg, 1.05 mmol) was dissolved in anhydrous THF (10 mL) in a 30 mL Schlenk flask. The solution was then cooled to -78°C, and n-BuLi hexane solution (1.6 mol / L, 0.59 mL, 0.94 mmol) was added dropwise. After the addition was complete, the mixture was stirred at -78°C for 15 minutes, and compound 13 (930 mg, 1.05 mmol) was added. After the addition, the mixture was raised to room temperature and stirred for 30 minutes. Further stirring was carried out at reflux temperature for 24 hours. After the reaction, methanol (0.6 mL) was added, and the reaction solution was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain dye 3 (180 mg, yield 15.4%).

[0311] The results of the NMR measurement of dye 3 are shown below. 1H-NMR(400MHz,CDCl3)δ7.90(d,2H),7.60(d,2H),7.28-7.40(m,8H),7.11(d,1H), 7.07(d,1H),6.95(d,2H),6.85(d,1H),6.83(d,1H),6.70(d,2H),6.47(t,1H),6.40 (dd,1H),6.35(s,2H),5.00(s,2H),3.81(t,2H),3.41(t,2H),3.26(t,4H),2.91(s, 3H),1.95(s,6H),1.86(s,6H),1.34(s,12H),0.91(t,6H),0.88(s,9H),0.02(s,6H)

[0312] <Synthesis of pigment 4>

[0313] [ka]

[0314] Under a nitrogen atmosphere, dye 3 (350 mg, 0.31 mmol) was dissolved in THF (7.65 mL) in a 100 mL flask and cooled to 0°C. Hydrogen chloride aqueous solution (4.0 mol / L, 2.3 mL, 9.18 mmol) was added dropwise while stirring. After the addition was complete, the temperature was raised to room temperature and stirred for 2 hours. After the reaction was complete, the mixture was neutralized with potassium carbonate and extracted with dichloromethane (50 mL x 3). The organic layer was washed with water (50 mL x 3), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to obtain dye 4 (311 mg, yield 98.7%).

[0315] The results of the NMR measurement of dye 4 are shown below. 1H-NMR(400MHz,CDCl3)δ7.89(d,2H),7.61(d,2H),7.27-7.42(m,8H),7.12(d ,1H),7.06(d,1H),6.96(d,2H),6.86(d,1H),6.83(d,1H),6.70(d,2H),6.47 (t,1H),6.40(dd,1H),6.35(s,2H),5.00(s,2H),3.81(t,2H),3.41(t,2H),3 .26(t,4H),2.91(s,3H),1.95(s,6H),1.86(s,6H),1.34(s,12H),0.91(t,6H)

[0316] <Synthesis of Compound 21>

[0317] [ka]

[0318] Under a nitrogen stream, a solution of 4-bromobenzyloxy-tert-butyldimethylsilane (50.0 g, 166 mmol) in THF (1.0 L) was cooled to -72°C in a 2 L three-necked flask, and n-BuLi hexane solution (1.6 mol / L, 114 mL, 182.6 mmol) was added dropwise over 25 minutes. After the addition was complete, the mixture was stirred at -72°C for 40 minutes. Then, at -72°C, a solution of dimethylformamide (DMF) (25.7 mL, 332 mmol) diluted with THF (25 mL) was added dropwise to the reaction solution over 15 minutes. After the addition, the mixture was stirred at 0°C for 2 hours, and then stirred at room temperature for another 2 hours. Then, water (500 mL) was added to the reaction solution at room temperature, and the mixture was stirred for 30 minutes. The product was extracted with ethyl acetate (1000 mL), the organic layer was washed with water (250 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel chromatography to obtain compound 21 (31.7 g, yield 76.4%).

[0319] <Synthesis of Compound 22>

[0320] [ka]

[0321] Under a nitrogen stream, in a 1 L three-necked flask, a solution of compound 21 (20.8 g, 83.1 mmol) and 2,2,2-trifluoro-1-phenylethane-1-one (28.9 g, 166.2 mmol) in THF (250 mL) was added to a solution of diazaabicycloundecene (DBU) (2.5 mL, 16.6 mmol) and 2-phenyl-6,7-dihydro-5H-pyrrole[2,1-c][1,2,4]2-triazolium chloride (1.84 g, 8.31 mmol) in THF (9 mL). The mixture was stirred at room temperature for 24 hours. Water (200 mL) was added to the reaction solution, and it was extracted with dichloromethane (100 mL x 3). The organic layer was washed with water (50 mL x 3), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 22 (22.4 g, yield 62.3%).

[0322] <Synthesis of Compound 23>

[0323] [ka]

[0324] Under a nitrogen atmosphere, compound 22 (0.90 g, 2.12 mmol) and malononitrile (0.70 g, 10.6 mmol) were dissolved in anhydrous THF (10 mL) in a 30 mL Schlenk flask and stirred at room temperature. Then, piperidine (0.63 mL, 6.4 mmol) and ethoxylithium (110 mg, 2.12 mmol) were added, and the mixture was stirred for 8 hours while heating to reflux temperature. After cooling to room temperature, precipitates were removed by filtration, and the recovered filtrate was concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 23 (400 mg, yield 36.2%).

[0325] <Synthesis of Compound 24>

[0326] [ka]

[0327] Under a nitrogen atmosphere, compound 23 (3.80 g, 8.04 mmol) and malononitrile (2.66 g, 40.2 mmol) were dissolved in anhydrous pyridine (20 mL) in a 100 mL three-necked flask. Molecular sieves 3A (5 g) were added to the solution, followed by the addition of acetic acid (230 mg, 4.02 mmol), and the mixture was stirred at room temperature for 96 hours. After removing the molecular sieves by filtration, the filtrate was flushed into water (200 mL) and extracted with dichloromethane (50 mL x 2). The organic layer was washed with water (20 mL x 3), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 24 (1.8 g, yield 42.9%).

[0328] <Synthesis of Compound 25>

[0329] [ka]

[0330] Under a nitrogen atmosphere, compound 24 (1.80 g, 3.45 mmol) was dissolved in anhydrous THF (100 mL) in a 300 mL three-necked flask and cooled to 0°C. A THF solution of tetra-n-butylammonium fluoride (TBAF) (1 mol / L, 3.80 mL, 3.80 mmol) was added to the solution, and the mixture was stirred at 0°C for 2 hours, followed by stirring at room temperature for 2 hours. After the reaction, saturated ammonium chloride solution (100 mL) was added to the reaction solution, and the mixture was extracted with dichloromethane (100 mL x 3). The organic layer was washed with water (100 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 25 (500 mg, yield 35.6%).

[0331] <Synthesis of Compound 26>

[0332] [ka]

[0333] Under a nitrogen atmosphere, compound 25 (500 mg, 1.23 mmol) was dissolved in anhydrous dichloromethane (30 mL) in a 100 mL three-necked flask and stirred at room temperature. Thionyl chloride (292 mg, 2.45 mmol) was added to the solution and stirred at room temperature for 12 hours. The organic layer was washed with water (50 mL x 2), dried over magnesium sulfate, filtered, and then concentrated under reduced pressure. The resulting crude compound was purified by silica gel column chromatography to obtain compound 26 (420 mg, yield 82.3%).

[0334] <Synthesis of Compound 27>

[0335] [ka]

[0336] Under a nitrogen atmosphere, compound 26 (200 mg, 4.70 mmol) and triphenylphosphine (616 mg, 2.35 mmol) were dissolved in anhydrous toluene (20 mL) in a 200 mL three-necked flask and stirred for 9 hours while heating to reflux temperature. After the reaction, the resulting white solid was collected by filtration, washed with toluene (20 mL), and dried under reduced pressure to obtain compound 27 (250 mg, yield 81.6%).

[0337] The results of the NMR measurement of compound 27 are shown below. 1 H-NMR(400MHz,CDCl3)δ7.78-7.73(m,9H), 7.64-7.58(m,7H),7.52(t,2H),7.33(t,2H),7.01(d,2H),5.82(dt,2H)

[0338] <Synthesis of pigment 5>

[0339] [ka]

[0340] Under a nitrogen stream, compound 27 (175 mg, 0.203 mmol) was dissolved in anhydrous THF (3 mL) in a 10 mL Schlenk flask. The solution was then cooled to -78°C, and n-BuLi hexane solution (1.6 mol / L, 0.11 mL, 0.18 mmol) was added. The mixture was then stirred at -78°C for 15 minutes, and compound 13 (140 mg, 1.05 mmol) was added. After the addition, the mixture was raised to room temperature and stirred for 30 minutes. Further stirring was carried out at reflux temperature for 24 hours. After the reaction, methanol (0.2 mL) was added, and the reaction solution was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain dye 5 (45 mg, yield 25.1%).

[0341] The results of the NMR measurement of dye 5 are shown below. 1 H-NMR(400MHz,CDCl3)δ8.10(d,2H), 7.80(d,2H),7.28-7.40(m,13H),7.13(d,1H),7.09(d,1H),6.96(d,2H),6 .87(d,1H),6.85(d,1H),6.73(d,2H),6.48(t,1H),6.40(dd,1H),6.35(s, 2H),5.00(s,2H),3.81(t,2H),3.41(t,2H),3.26(t,4H),2.91(s,3H),1.9 5(s,6H),1.86(s,6H),1.34(s,12H),0.91(t,6H),0.87(s,9H),0.01(s,6H)

[0342] <Synthesis of base polymer 1>

[0343] [ka]

[0344] Methyl methacrylate (MMA) (12.8 g, 127.8 mmol), 1-adamantyl methacrylate (28.2 g, 128.0 mmol), and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (16.1 g, 64.1 mmol) were dissolved in deoxygenated toluene (110 mL), then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (171 mg, 0.69 mmol) was added. Thereafter, the reaction solution was heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C, and the mixture was further stirred for 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (120 mL), and the resulting solid was collected by filtration. The filtered solid was rinsed and washed with hexane (120 mL), and vacuum-dried to obtain Base Polymer 1 (35.0 g, yield 61%).

[0345] The molecular weight of the obtained Base Polymer 1 was determined by GPC using a GPC system manufactured by Shimadzu Corporation (liquid delivery system: LC-20AD, detector: RID) (columns: 2 columns of TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S), TSKguardcolumn SuperMP(HZ)-M, developing solvent: THF, column temperature: 40°C). As a result, the weight average molecular weight Mw was 114000, and the number average molecular weight Mn was 34000.

[0346] <Synthesis of EO Polymer 1> EO Polymer 1, which is a polymer compound containing a group obtained by removing one hydrogen atom from Dye 4, was synthesized by the following steps.

[0347] [Chemical Formula]

[0348] Under a nitrogen atmosphere, base polymer 1 (1.31 g) and dye 4 (300 mg) were dissolved in dehydrated 1,4-dioxane (39 mL), and dibutyltin dilaurate (DBTDL) (129 μL) was added. The mixture was stirred in a 110°C water bath for 3 hours. Then, dehydrated methanol (2.04 mL) and dibutyltin dilaurate (DBTDL) (129 μL) were added, and the mixture was stirred in a 110°C water bath for 2 hours. After cooling to room temperature, the reaction solution was added dropwise to hexane (300 mL), and the resulting solid was filtered off. The filtered solid was purified by activated clay treatment (solvent: dichloromethane) and reprecipitation (rich solvent: dichloromethane, poor solvent: methanol), and vacuum-dried under heating at 60°C to obtain EO polymer 1 (1.2 g).

[0349] The content of the group obtained by removing one hydrogen atom from dye 4 in the obtained EO polymer 1 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer. The content of the group obtained by removing one hydrogen atom from dye 4 relative to the mass of EO polymer 1 was 23% by mass.

[0350] <Synthesis of Compound 28>

[0351] [ka]

[0352] Under a nitrogen atmosphere, 2-(methylamino)ethane-1-ol (167.7 g, 2.23 mol) and imidazole (253.3 g, 3.72 mol) were dissolved in dichloromethane (2.8 L) in a 5 L flask and cooled to 0°C. After cooling, tert-butylchlorodimethylsilane (280.3 g, 1.86 mol) was added to the solution and stirred at room temperature for 2 hours. After the reaction, the organic layer was washed with water (500 mL x 3), dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain compound 28 (323.7 g, yield 91.9%).

[0353] <Synthesis of Compound 29>

[0354] [ka]

[0355] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 28 (19.4 g, 102.6 mmol) and 1-(benzyloxy)-3-bromobenzene (22.5 g, 85.5 mmol) in toluene (225 mL) was added. Sodium tert-butoxide (18.1 g, 188.1 mmol), Pd2(dba)3 (786 mg, 0.86 mmol), and (4-dimethylaminophenyl)di-tert-butylphosphine (Amphos) (913 mg, 3.44 mmol) were then added, and the mixture was stirred at 100 °C for 4.5 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 29 (22.2 g, yield 69.9%).

[0356] <Synthesis of Compound 30>

[0357] [ka]

[0358] Under a nitrogen atmosphere, compound 29 (22.2 g, 59.7 mmol) was dissolved in DMF (222 mL) in a 500 mL three-necked flask. After cooling to 0°C, N-bromosuccinimide (NBS) (10.6 g, 59.7 mmol) was added. The reaction solution was then heated to room temperature and stirred for 3 hours. After the reaction, water (200 mL) was added to the reaction solution and extracted with ethyl acetate (500 mL). The organic layer was washed with water (50 mL x 3), dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 30 (24.3 g, yield 90.4%).

[0359] <Synthesis of Compound 31>

[0360] [ka]

[0361] Under a nitrogen stream, compound 30 (7.0 g, 15.5 mmol) was dissolved in THF (70 mL) in a 300 mL three-necked flask and cooled to -78 °C. While stirring the solution at -78 °C, n-BuLi hexane solution (1.6 mol / L, 10.7 mL, 17.1 mmol) was added. After addition, the mixture was stirred at -78 °C for 30 minutes, and a solution of DMF (4.54 g, 62.2 mmol) diluted with THF (4.5 mL) was added dropwise. After addition, the reaction solution was raised to room temperature and stirred at room temperature for 2 hours. After the reaction, water (100 mL) was added to the reaction solution and extracted with ethyl acetate (300 mL). The organic layer was washed with water (50 mL x 3), dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 31 (4.24 g, yield 68.3%).

[0362] <Synthesis of pigment 6>

[0363] [ka]

[0364] Under a nitrogen atmosphere, compound 31 (0.5 g, 1.25 mmol) and a solution of 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (513 mg, 1.63 mmol) in THF (10 mL) were added to a 100 mL three-necked flask, to which ethanol (20 mL) was added and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain dye 6 (0.43 g, yield 49.3%).

[0365] The results of the NMR measurement of dye 6 are shown below. 1 H-NMR(400MHz,CDCl3)δ8.10(d,1H),7.24-7.46(m,11H),6.90(d,1H),6.40(dd,1H),6.1 0(d,1H),5.05(dd,2H),3.78(t,2H),3.60(t,2H),3.16(s,3H),0.86(s,9H),0.02(s,6H)

[0366] <Synthesis of Compound 32> Compound 32 described below was synthesized by the same method as N,N-dibutyl-N-[4-2-(2-thienyl)vinyl]phenylamine described in Patent Document 2.

[0367] [ka]

[0368] <Synthesis of pigment 7>

[0369] [ka]

[0370] Under a nitrogen atmosphere, a solution of compound 32 (19.0 g, 0.606 mol) in DMF (300 mL) was slowly added dropwise to a solution of tetracyanoethylene (9.32 g, 0.727 mol) in DMF (100 mL) in a 1 L three-necked flask, and the mixture was stirred at room temperature for 24 hours. After the reaction was complete, the solution was poured into ice water (4 L), the resulting solid was filtered off and washed with water (200 mL). The organic layer obtained by dissolving the solid in dichloromethane (200 mL) was washed with water (100 mL) and saturated brine (100 mL), concentrated under reduced pressure, and purified by silica gel chromatography to obtain pigment 7 (8.20 g, yield 32.6%).

[0371] <Evaluation device> The following equipment was used for the evaluation below. • Spin coater: Mikasa Corporation MS-A150 • Hot plate: AS ONE Corporation HP-1SA • Oven: ESPEC Corporation STH-120 small high-temperature chamber • Film thickness measurement: VertScan optical interferometer manufactured by Hitachi High-Tech Corporation. • Gold deposition: ULVAC, Inc. EX-400-C08 • Vacuum constant temperature drying oven: DP-23, manufactured by Yamato Scientific Co., Ltd. • Temperature controller: Lake Shore Cryotronics Model 3060 • Voltage application device: KEITHLEY 2470 Source Meter • Laser light source: TSL-570 manufactured by Santec Corporation • Function Generator: Teledyne LeCroy T3AFG10 • Lock-in amplifier: Digital lock-in amplifier LI5600 manufactured by NF Circuit Design Block Co., Ltd. • Spectrophotometer: Hitachi, Ltd. U-4100

[0372] [Example 1] [Evaluation of maximum absorption wavelength] The synthesized nonlinear optical material, dye 2, was dissolved in chloroform, and its absorption spectrum (250-2000 nm) in chloroform was evaluated using a spectrophotometer. The longest wavelength among the maximum wavelengths was defined as the maximum absorption wavelength. The obtained maximum absorption wavelengths are shown in Table 2.

[0373] (Cleaning of ITO substrate) A thin-film ITO substrate manufactured by EHC Corporation (a 0.7 mm thick glass plate with a 9 nm thick ITO film on one side; sheet resistance on the ITO film side: 519~578 Ω / □) was cleaned in ultrapure water using an ultrasonic cleaner to obtain an ITO substrate for coating a nonlinear optical material composition. Here, the glass plate contained in the ITO substrate corresponds to the support, and the ITO film corresponds to the electrode.

[0374] (Preparation of substrates with an intermediate layer film) A compound represented by the following structural formula (hereinafter also referred to as "Material 1") was dissolved in cyclohexanone to a concentration of 3% by mass, and the mixture was filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm to obtain intermediate layer composition A. Intermediate layer composition A was coated onto the side of the ITO substrate where the ITO film was provided using a spin coater.

[0375] After coating an ITO substrate with intermediate layer composition A, it was pre-baked on a hot plate at 60°C for 1 minute, and then heat-treated in an oven at 230°C for 30 minutes to cure the intermediate layer composition A, thereby obtaining a substrate with an intermediate layer film formed on the ITO substrate. The thickness of the obtained film (intermediate layer thickness) is shown in Table 2.

[0376] [ka]

[0377] (Creation of membrane 1) Composition 1 was obtained by mixing dye 2, a nonlinear optical material, with PMMA to the mass concentration (dye concentration) shown in Table 2 in terms of solid content, and then dissolving these in cyclohexanone to a total solid content concentration of 13% by mass, and filtering through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm. Composition 1 was coated onto the side of a substrate with an intermediate layer film that has the intermediate layer using a spin coater.

[0378] A substrate coated with the above composition 1 was pre-baked on a hot plate at 60°C for 2 minutes, and then the solvent was removed by heat drying in a vacuum constant-temperature drying oven at 85°C for 15 hours to obtain a substrate (substrate 1) on which a nonlinear optical layer was formed. The thickness of the nonlinear optical layer was measured. The thickness of the nonlinear optical layer (EO material thickness) is shown in Table 2. The resulting film 1 had a sufficient thickness to exhibit nonlinear optical effects in devices such as optical modulators and optical switches.

[0379] (Creation of electrode-equipped substrates) For the nonlinear optical layer surface of the fabricated substrate, the film thickness was 50 nm and the area was 30 mm². 2 Gold electrodes were formed by depositing gold in a circular shape, and an electrode-equipped substrate was obtained. The electrode-equipped substrate had the following layer structure and was used to evaluate the electro-optic effect. Layer structure: ITO substrate (glass plate support + ITO film) / intermediate layer / film containing nonlinear optical material / gold electrode

[0380] [Polling process] The prepared electrode-equipped substrate was heated to 115°C using a temperature controller, and then cooled to room temperature with liquid nitrogen while applying a polling voltage of 100V / μm using a voltage application device, thereby obtaining a polled substrate in which the nonlinear optical material on the electrode-equipped substrate was field-oriented.

[0381] [Electro-optic effect measurement] The electro-optic coefficient (r33) at a wavelength of 1.31 μm was measured on the prepared polled substrates using a method similar to that disclosed by CCTeng et al., Appl. Phys. Lett., 56, p1734 (1990), and Y. Shuto et al., J. Appl. Phys., 77, p4632 (1995). The results are shown in Table 2.

[0382] [Evaluation of the electro-optic effects of dyes] To compare the electro-optic effects of each dye, we defined EOMW / mass% using the following formula, which corrects the electro-optic coefficient (r33) for the dye (group) concentration and dye (group) molecular weight, and used it for evaluation. The results are shown in Table 2. EOMW / mass% = Electro-optic coefficient × Molecular weight of dye (group) / Mass concentration of dye (group)

[0383] EOMW / mass% corresponds to the electro-optic coefficient normalized by the number of moles of pigment (group) contained in the sample. Even if the pigment (group) concentration and molecular weight in the sample differ, a larger EOMW / mass% indicates a greater electro-optic effect of the pigment itself.

[0384] [Example 2] The data in Table 2 was obtained in the same manner as in Example 1, except that dye 3 was used as the nonlinear optical material.

[0385] [Example 3] The data in Table 3 was obtained in the same manner as in Example 1, except that dye 5 was used as the nonlinear optical material.

[0386] [Example 4] The data in Table 2 was obtained in the same manner as in Example 1, except that dye 1 was used as the nonlinear optical material.

[0387] [Example 5] The data in Table 2 was obtained in the same manner as in Example 1, except that EO polymer 1 was used as the nonlinear optical material.

[0388] [Comparative Example 1] The data in Table 2 was obtained in the same manner as in Example 1, except that dye 6 was used as the nonlinear optical material.

[0389] [Comparative Example 2] The data in Table 3 was obtained in the same manner as in Example 1, except that dye 7 was used as the nonlinear optical material.

[0390] [Table 2]

[0391] [Table 3]

[0392] Figure 1 shows the relationship between the maximum absorption wavelength and EOMW / mass% for Examples 1-5 and Comparative Examples 1-2.

[0393] As shown in Tables 2 and 3 and Figure 1, compared to dye 6 (Comparative Example 1), which has a similar maximum absorption wavelength, dyes 2 (Example 1), 3 (Example 2), 1 (Example 4), and EO polymer 1 (Example 5) showed higher electro-optic coefficients per molecule (EOMW / mass%). Furthermore, compared to dye 7 (Comparative Example 2), which has a similar maximum absorption wavelength, dye 5 (Example 3) showed a higher electro-optic coefficient per molecule (EOMW / mass%). In other words, it was found that the compounds or polymer compounds according to the embodiments of the present invention can be used to obtain a high electro-optic effect per molecule relative to the maximum absorption wavelength. [Industrial applicability]

[0394] The compounds, polymer compounds, and compositions according to the embodiments of the present invention can exhibit higher electro-optic effects in wavelengths shorter than the C-band compared to dyes with similar maximum absorption wavelengths. Therefore, they can be used, for example, as materials for the core layer of a waveguide in an electro-optic element including a waveguide structure.

Claims

1. A compound represented by the following formula (1). 【Chemistry 1】 [In formula (1), Ar １１ Each of these is independently a divalent aromatic group which may have substituents, R １１ and R １３ 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. R １２ and R １４ Each of these is independently a hydrogen atom, a group selected from the following optionally substituted hydrocarbon group A, an optionally substituted aromatic group, an optionally substituted amino group, a hydroxyl group, or a halogen atom. Y １１ Each is independently a divalent π-conjugated linkage group which may have substituents, where Y １１ At least one of them is a vinylene group which may have substituents, S １１ This is a divalent aromatic group which may have substituents, Z １１ is a group represented by the following formula (2), I understand １１ Each of these is an integer between 0 and 5, independently of the others. I understand １２ These are integers from 1 to 5, I understand １３ is an integer from 0 to 5, n １１ [This is an integer between 1 and 15.] 【Chemistry 2】 [In formula (2), *J ２１ is, S １１ This is the bonding position with, R ２１ and R ２２ 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, and R ２１ and R ２２ They may be bonded together to form a ring, or R ２１ and R ２２ R ２１ and R ２２ These may also form a carbonyl group together with the carbon atom to which they are bonded. R ２３ and R ２４ Each of these is independently a cyano group, a C2-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents. X ２１ is an oxygen atom, a sulfur atom, or N-Q ２１ And, Q ２１ This is a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. <Hydroxide 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, wherein 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. S in formula (1) １１ The compound according to claim 1, wherein the compound is a divalent aromatic group having 3 to 10 carbon atoms, which may have substituents.

3. Y in formula (1) １１ At least one of them is independently represented by the following formula (3), where n in formula (1) is １１ If it is 2 or more, then R in formula (3) below ３１ and R ３２ is, other Y １１ R included ３１ or R ３２ The compound according to claim 1, which may be linked to form a ring. 【Transformation 3】 [In formula (3), R ３１ and R ３２ 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R ３１ and R ３２ They may be joined together to form a ring.

4. Y in formula (1) １１ However, each can be expressed independently by the following equations (4), (5), or (6): Y １１ At least one of them is expressed by the following equation (4), However, n in formula (1) １１ If it is 2 or more, Y １１ R inside ４１ , R ４２ , R ５１ , R ５２ , and R ６１ ~R ６７ is, other Y １１ R included ４１ , R ４２ , R ５１ , R ５２ , or R ６１ ~R ６７ The compound according to claim 1, which may be linked to form a ring. 【Chemistry 4】 [In formula (4), R ４１ and R ４２ 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R ４１ and R ４２ They may be joined together to form a ring. 【Transformation 5】 [In formula (5), R ５１ and R ５２ 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R ５１ and R ５２ They may be bonded together to form a ring. X ５１ is an oxygen atom, a sulfur atom, or N-Q ５１ And, Q ５１ This is 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 which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, or a boryl group which may have substituents. 【Transformation 6】 [In formula (6), R ６１ ~R ６７ 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 hydroxyl group which may have substituents, an amino group which may have substituents, a thiol group which may have substituents, a cyano group which may have substituents, a halogen atom which may have substituents, and R ６１ ~R ６７ At least two of them may be joined together to form a ring.

5. n in formula (1) １１ The compound according to claim 1, wherein is an integer from 2 to 5.

6. A composition comprising a compound according to any one of claims 1 to 5 and a polymer material.

7. The composition according to claim 6, wherein the polymer material is at least one selected from the group consisting of poly(meth)acrylic acid ester, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, and copolymers thereof.

8. The composition according to claim 6, comprising an organic solvent.

9. A nonlinear optical element comprising the compound described in any one of claims 1 to 5.

10. A nonlinear optical element according to claim 9, which operates based on the electro-optic effect.

11. An optical modulator comprising the nonlinear optical element described in claim 9.

12. A polymer compound comprising, as at least one selected from the substituent and the main chain, a group obtained by removing at least one hydrogen atom from the compound represented by the following formula (1). 【Transformation 7】 [In formula (1), Ar １１ Each of these is independently a divalent aromatic group which may have substituents, R １１ and R １３ 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. R １２ and R １４ Each of these is independently a hydrogen atom, a group selected from the following optionally substituted hydrocarbon group A, an optionally substituted aromatic group, an optionally substituted amino group, a hydroxyl group, or a halogen atom. Y １１ Each is independently a divalent π-conjugated linkage group which may have substituents, where Y １１ At least one of them is a vinylene group which may have substituents, S １１ This is a divalent aromatic group which may have substituents, Z １１ This is a group represented by the following formula (2), I understand １１ Each of these is an integer between 0 and 5, independently of the others. I understand １２ These are integers from 1 to 5, I understand １３ is an integer from 0 to 5, n １１ [This is an integer between 1 and 15.] 【Transformation 8】 [In formula (2), *J ２１ is, S １１ This is the bonding position with, R ２１ and R ２２ are each independently a group selected from the following hydrocarbon group group A which may have a substituent, or an aromatic group which may have a substituent, and R ２１ and R ２２ may be bonded to each other to form a ring, or R ２１ and R ２２ may form a carbonyl group together with R ２１ and R ２２ and the carbon atom to which these are bonded, R ２３ and R ２４ are each independently a cyano group, an optionally substituted alkyloxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted alkylsulfonyl group having 1 to 10 carbon atoms, X ２１ is an oxygen atom, a sulfur atom, or N-Q ２１ And, Q ２１ This is a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. <Hydroxide 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, wherein part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group, and / or a silicon atom.

13. The group obtained by removing at least one hydrogen atom from the compound represented by formula (1) is R １４ The polymer compound according to claim 12, which is a group from which a hydrogen atom has been removed.

14. A nonlinear optical element comprising the polymer compound described in claim 12 or 13.

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

16. An optical modulator comprising the nonlinear optical element described in claim 14.

Images