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

Abstract

The purpose of the present invention is to provide: a polymer compound with improved filterability and excellent thermal stability by suppressing a viscosity increase and gelation during heating; a composition containing the polymer compound; a nonlinear optical element using the composition; and an optical modulator that is provided with the nonlinear optical element and that operates on the basis of an electro-optic effect. The present invention relates to a polymer compound containing a repeating unit represented by formula (1). (Definitions of groups are set forth in the description.)　

Description

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

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

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

[0003] Nonlinear optical materials, particularly organic nonlinear optical materials, are generally obtained by mixing or bonding compounds (dyes) having nonlinear optical activity to polymer materials such as polymethyl methacrylate (PMMA). Nonlinear optical properties are expressed by the electro-optic coefficient (hereinafter also referred to as the "EO coefficient" in this specification), and are also denoted as r33. As dyes, so-called push-pull type π-conjugated compounds are known, which have electron-donating groups and electron-withdrawing groups located at both ends of the molecular structure, and a π-conjugated chain connecting them.

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

[0005] For example, Patent Document 5 discloses a nonlinear optically active copolymer in which a dye having nonlinear optical activity is introduced via an isocyanate group into a polymer material having a high glass transition temperature, thereby suppressing the relaxation of the orientation state of the dye due to heat. Patent Document 6 discloses a nonlinear optically active copolymer in which a dye having nonlinear optical activity is introduced to the benzene ring of the side chain of polystyrene via a phenyl ester bond.

[0006] However, when isocyanate groups are used as bonding groups between polymer materials and dyes with nonlinear optical activity, for example, in the process of heat-drying (solvent removal) a polymer material into which a dye with nonlinear optical activity has been introduced via isocyanate groups, the isocyanate groups generated by the detachment of the dye from the polymer material react with moisture in the solvent or other isocyanate groups to form a network structure, increasing viscosity due to the increase in molecular weight and leading to gelation, thus causing problems with thermal stability. Furthermore, the dye introduced via isocyanate groups is transmitted via urethane bonds, and the deterioration of these urethane bonds over time due to moisture in the atmosphere and heat also contributes to reduced thermal stability. In addition, when ester bonds or urethane bonds are used as bonding groups between polymer materials and dyes with nonlinear optical activity, it is generally known that moisture in the atmosphere reacts with the carbonyl groups in the bond, gradually leading to hydrolysis, which can reduce the thermal stability of nonlinear optically active polymer compounds, including nonlinear optically active copolymers. Furthermore, since this reaction is accelerated by ambient temperature conditions, the dye portion is released from the nonlinear optically active polymer compound, reducing the orientation of the dye and thus lowering the thermal stability of the nonlinear optical element.

[0007] International Publication No. 2019 / 151318, Japanese Patent Publication No. 2010-066325, International Publication No. 2011 / 024774, Japanese Patent Publication No. 2015-178544, International Publication No. 2017 / 159815, International Publication No. 2004 / 065615

[0008] The object of the present invention is to provide a polymer compound with improved filterability and excellent thermal stability by suppressing viscosity increase and gelation during heating, and in addition, to provide a composition containing the polymer compound. Another object of the present invention is to provide a nonlinear optical element using the above composition, and to provide an optical modulator equipped with the nonlinear optical element that operates based on the electro-optic effect.

[0009] As a result of intensive studies in view of the above problems, the present inventors have found that by making the binding site between a polymer material and a compound (dye) having non-linear optical activity have a specific structure, an increase in viscosity and gelation during heating are suppressed, and furthermore, by using a highly heat-resistant linking group, high thermal stability is exhibited, leading to the completion of the present invention.

[0010] The gist of the present invention is as follows.

[0011] Aspect 1 of the present invention relates to a polymer compound containing a repeating unit represented by the following formula (1).

[0012]

[0013] [In formula (1), A １１ represents a trivalent group obtained by removing two hydrogen atoms from a group selected from the following hydrocarbon group A which may have a substituent, a trivalent aromatic group which may have a substituent, a trivalent heterocyclic group which may have a substituent, or a trivalent amino group which may have a substituent, A １２ and A １３ each independently represent a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A which may have a substituent, a divalent aromatic group which may have a substituent, or a divalent heterocyclic group which may have a substituent, a carbonyl group, or an oxygen atom, R １１ each independently represent a group selected from the following hydrocarbon group A which may have a substituent, or an aromatic group which may have a substituent, and when n １２ is 2 or more, the R １１ may be bonded to another R １１ to form a ring, L １１ each independently represent a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A which may have a substituent, an oxygen atom, a carbonyl group, a divalent aromatic group which may have a substituent, or a divalent heterocyclic group which may have a substituent, X １１ each independently represent a group obtained by removing one hydrogen atom from a compound represented by the following formula (2), n １１ is an integer of 1 to 5, n １２ is an integer of 0 to 4, n１３ n is an integer between 0 and 5. １４ and n １５ Each of these is an integer between 0 and 5, where n is independent. １１ to n １２ The sum of the numbers is 5 or less.

[0014]

[0015] [In formula (2), Ar ２１ Each of these is independently a divalent aromatic group which may have substituents, and R ２１ and R ２３ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A, which may have substituents, or a divalent aromatic group which may have substituents, and R ２２ and R ２４ Each independently represents a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ２１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ２１ This is a group represented by the following formula (3), and m ２１ Each of these is an integer between 0 and 5, and m ２２ m is an integer between 1 and 5. ２３ n is an integer between 0 and 5. ２１ [This is an integer between 1 and 15.]

[0016]

[0017] [In formula (3), *J ３１ Y ２１ This represents the bonding position with R ３１ and R ３２ Each independently represents a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, R ３１ and R ３２ They may be bonded together to form a ring, or R ３１ and R ３２ R ３１ and R３２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ３３ ~R ３５ Each independently represents a cyano group, a C2-C30 alkyloxycarbonyl group which may have substituents, or a C1-C30 alkylsulfonyl group which may have substituents, X ３１ is an oxygen atom, a sulfur atom, or N-Q ３１ This represents Q ３１ represents a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. ] <Hydrogen group A> A branched, linear or cyclic alkyl group having 1 to 30 carbon atoms, a branched, linear or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, linear or cyclic alkynyl group having 2 to 30 carbon atoms, in which part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group and / or a silicon atom.

[0018] Aspect 2 of the present invention is a polymer compound of aspect 1, wherein Y in formula (2) ２１ At least one of them is independently represented by the following formula (4), where n in formula (2) is ２１ If the number is 2 or more, the Y ２１ R inside ４１ and R ４２ is, other Y ２１ R included ４１ or R ４２ This relates to polymer compounds that may be linked together to form a ring.

[0019]

[0020] [In formula (4), R ４１ and R ４２ Each independently represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ４１ and R ４２ They may be joined together to form a ring.

[0021] A third aspect of the present invention is a polymer compound of the first or second aspect, wherein Y in formula (2) ２１ At least one of these is independently represented by the following formula (5), formula (6), or formula (7), provided that n in formula (2) is ２１ If the number is 2 or more, the Y ２１ R inside ５１ , R ５２ , R ６１ , R ６２ , and R ７１ ~R ７７ is, other Y ２１ R included ５１ , R ５２ , R ６１ , R ６２ , or R ７１ ~R ７７ This relates to polymer compounds that may be linked together to form a ring.

[0022]

[0023] [In formula (5), R ５１ and R ５２ Each independently represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ５１ and R ５２ They may be joined together to form a ring.

[0024]

[0025] [In formula (6), R ６１ and R ６２ Each independently represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ６１ and R ６２ They may be joined together to form a ring, X ６１ is an oxygen atom, a sulfur atom, or N-Q ６１ This represents Q６１ represents a hydrogen atom, a group selected from the group of hydrocarbon groups A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent.

[0026]

[0027] [In formula (7), R ７１ ~R ７７ each independently represents a hydrogen atom, a group selected from the group of hydrocarbon groups A which may have a substituent, an aromatic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, a thiol group, a cyano group, a halogen atom, or a boryl group which may have a substituent, and further, at least two of R ７１ ~R ７７ may be bonded to form a ring. ] [[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Aspect 5 of the present invention relates to a polymer compound in any one of Aspects 1 to 4, further comprising a repeating unit represented by the following formula (11).

[0034]

[0035] [In formula (11),R １１１ to R １１６ are each independently a hydrogen atom or a group selected from the hydrocarbon group A which may have a substituent,L [[ID=]11] １１１ and L １１２ are each independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have a substituent, an oxygen atom, a carbonyl group, a divalent aromatic group which may have a substituent, or a divalent heterocyclic group which may have a substituent, Y １１１ and Y １１２ are each independently a hydrogen atom, a group selected from the hydrocarbon group A which may have a substituent, an aromatic group which may have a substituent, or a heterocyclic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, or a silyl group which may have a substituent, R １１３ to R １１６ , L １１１ and L １１２ may be bonded to each other to form a ring, n １１１ and n １１２ are each independently an integer of 0 to 5. ]

[0036] Aspect 6 of the present invention relates to a composition comprising any one of the polymer compounds of Aspects 1 to 5 and an organic solvent.

[0037] Aspect 7 of the present invention relates to a non-linear optical element comprising a film containing any one of the polymer compounds of Aspects 1 to 5.

[0038] Aspect 8 of the present invention relates to the non-linear optical element of Aspect 7, which operates based on an electro-optical effect.

[0039] n Aspect 9 of the present invention relates to an optical modulator comprising the non-linear optical element of Aspect 7 or 8.

[0040] The present invention provides a polymer compound with improved filterability and excellent thermal stability due to the suppression of viscosity increase and gelation during heating, and also provides a composition containing the polymer compound. Furthermore, the present invention provides a nonlinear optical element using the above composition, and provides an optical modulator equipped with the nonlinear optical element that operates based on the electro-optic effect.

[0041] <Explanation of Terms> The terms used in this specification are explained below.

[0042] <Polymer Compounds> In this specification, polymer compounds refer to compounds having a molecular weight of 2000 or more and containing four or more repeating units in the molecule. Polymer compounds are not particularly limited, but are preferably polymers, and may be homopolymers, block copolymers, random copolymers, alternating copolymers, or graft copolymers, or in other forms.

[0043] <Copolymer> A copolymer is a polymer compound that has two or more repeating units in its molecule.

[0044] <Substituents> Unless otherwise specified, substituents are any group, but preferably the substituent group W described below. １ The group is selected from the substituent group W. The substituents that may be present are also the substituent group W. １ If it is stated that selection from is preferable, the preferred substituents are also the substituent group W below. １ As stated therein.

[0045] <Substituent group W １ > Substituent group W １This group consists of hydroxyl groups, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aromatic oxy groups, aralkyloxy groups, alkylthio groups, aromatic thio groups, aralkylthio groups, alkyloxycarbonyl groups, dialkylamino groups, diarylamino groups, arylalkylamino groups, acyl groups, halogen atoms, haloalkyl groups, 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.

[0046] Substituent group W １ More specifically, the following structures can be cited, from the [alkyl group] to the [bonding of adjacent substituents].

[0047] [Alkyl groups] Alkyl groups are linear, branched, or cyclic, and have one or more carbon atoms, preferably four or more, usually 24 or less, preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group, adamantyl group, etc.

[0048] [Alkenyl group] An alkenyl group is linear, branched, or cyclic, and usually has two or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include vinyl groups.

[0049] [Alkynyl group] The alkynyl group is linear or branched, usually has two or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include the ethynyl group.

[0050] [Alkyloxy Groups] Alkyloxy groups are linear, branched, or cyclic, have one or more carbon atoms, and usually have 24 or fewer carbon atoms, preferably 12 or fewer. Specific examples include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, dodecyloxy group, adamantyloxy group, etc.

[0051] [Aromatic oxy group] The aromatic oxy group has four or more carbon atoms, preferably five or more, and usually 36 or fewer, preferably 24 or fewer. Specific examples include the phenoxy group, naphthoxy group, and pyridyloxy group.

[0052] [Aralkyloxy group] The aralkyloxy group has four or more carbon atoms, preferably five or more, and is usually 50 or less, preferably 30 or less. Specific examples include benzyloxy group, tolylmethoxy group, thiophenylmethoxy group, 2-phenylethyloxy group, 2-phenylpropyl-2-yloxy group, 2-phenylbutyl-2-yloxy group, 3-phenylpentyl-3-yloxy group, 3-phenyl-1-propyloxy group, 4-phenyl-1-butyloxy group, 5-phenyl-1-pentioxyl group, 6-phenyl-1-hexyloxy group, 7-phenyl-1-heptyloxy group, 8-phenyl-1-octyloxy group, etc.

[0053] [Alkylthio group] An alkylthio group has one or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, n-hexylthio group, cyclohexylthio group, dodecylthio group, adamantylthio group, etc.

[0054] [Aromatic Thio Groups] Aromatic thio groups have three or more carbon atoms, preferably four or more, and usually 50 or fewer, preferably 30 or fewer. Specifically, examples include phenylthio groups, naphthylthio groups, pyridylthio groups, etc.

[0055] [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.

[0056] [Alkyloxycarbonyl group] The alkyloxycarbonyl group has two or more carbon atoms, usually 24 or less, preferably 12 or less. Specific examples include the methoxycarbonyl group and the ethoxycarbonyl group.

[0057] [Dialkylamino group] A dialkylamino group has two or more carbon atoms, usually 24 or fewer, preferably 12 or fewer. Specific examples include dimethylamino group and diethylamino group.

[0058] [Amino Group] The amino group may have substituents, preferably a secondary amino group or a tertiary amino group, and more preferably a tertiary amino group. Preferred substituents on the amino group are alkyl groups, cycloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the amino group, they may be the same or different, and they may bond to each other to form a ring with the nitrogen atom to which each is bonded. Specific examples include dimethylamino group, diethylamino group, ethylmethylamino group, n-propylmethylamino group, di-iso-propylamino group, di-n-butylamino group, di-n-hexylamino group, di-n-butylamino group, methylphenylamino group, ethylphenylamino group, butylphenylamino group, hexylphenylamino group, diphenylamino group, 2,6-dimethylphenylphenylamino group, and 2,4,6-trimethylphenylphenylamino group.

[0059] [Halogen atoms] Halogen atoms are typically fluorine, chlorine, bromine, or iodine atoms. More preferably, fluorine atoms.

[0060] [Haloalkyl groups] Haloalkyl groups have one or more carbon atoms, usually 12 or fewer, preferably 6 or fewer. Specific examples include trifluoromethyl groups and chloromethyl groups, with trifluoromethyl groups being more preferred.

[0061] [Silicone group] A silyl group typically has two or more carbon atoms, preferably three or more, and typically 36 or fewer carbon atoms, preferably 24 or fewer. Specific examples include trimethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, etc.

[0062] [Siloxy group] The siloxy group has two or more carbon atoms, preferably three or more, and is usually 36 or less, preferably 24 or less, and more preferably 18 or less. Specific examples include the trimethylsiloxy group, tert-butyldimethylsiloxy group, tert-butyldiphenylsiloxy group, and triphenylsiloxy group.

[0063] [Aralkyl Groups] Aralkyl groups typically have 7 or more carbon atoms, preferably 9 or more, and typically 30 or less, preferably 18 or less, and more preferably 10 or less. Specific examples include benzyl group, 2-phenylethyl group, 2-phenylpropyl-2-yl group, 2-phenylbutyl-2-yl group, 3-phenylpentyl-3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, and 8-phenyl-1-octyl group. [Aromatic Hydrocarbon Groups] Aromatic hydrocarbon groups typically have 6 or more carbon atoms, and typically 36 or less, preferably 24 or less. Specific examples include phenyl group, naphthyl group, and groups in which multiple phenyl groups are linked together.

[0064] [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.

[0065] [Shape of substituents] The substituents may include any of the following structures: linear, branched, or cyclic.

[0066] [Bonding of adjacent substituents] When the above substituents are adjacent, adjacent substituents may bond to each other to form a ring. Preferred ring sizes are four-membered rings, five-membered rings, and six-membered rings. Specific examples include cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0067] <Alkyl groups> Alkyl groups may have substituents, and may be linear, branched, or cyclic. While the number of carbon atoms is generally not limited, it is preferably between 1 and 30 carbon atoms, more preferably 20 carbon atoms or less, and even more preferably 10 carbon atoms or less. Specific examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, dodecyl, and adamantyl groups. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0068] <Aromatic Hydrocarbon Groups> Aromatic hydrocarbon groups refer to monovalent, divalent, or trivalent or more structures of hydrocarbon aromatic ring structures, depending on their bonding state within the structure of the compounds described below. The number of carbon atoms in an aromatic hydrocarbon group is not usually limited, but is preferably 6 to 60 carbon atoms, more preferably 48 carbon atoms or less, and even more preferably 30 carbon atoms or less. Specifically, examples include monocyclic rings or fused ring groups containing 2 to 5 rings, such as benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings, or structures in which multiple groups selected from these are linked together. When multiple aromatic hydrocarbon groups are linked together, a structure with 2 to 10 linked groups is usually given, and a structure with 2 to 5 linked groups is preferred. When multiple aromatic hydrocarbon groups are linked together, the same structure may be linked, or different structures may be linked. The substituents that these groups may have are the substituent group W. １ Selected from.

[0069] <Aromatic Heterocyclic Groups> Aromatic heterocyclic groups refer to monovalent, divalent, or trivalent or more heteroaromatic ring structures, depending on their bonding state within the structure of the compounds described below. While the number of carbon atoms in an aromatic heterocyclic group is not usually limited, it is preferably between 3 and 50 carbon atoms, more preferably 45 carbon atoms or less, and even more preferably 30 carbon atoms or less. Specifically, examples include monocyclic rings with 5 to 6 members or fused ring groups containing 2 to 4 rings, such as furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienopyrrole rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, sinnoline rings, quinoxaline rings, phenanthridine rings, perimidine rings, quinazoline rings, and quinazolinone rings, or groups in which multiple such groups are linked. When multiple aromatic heterocyclic groups are linked, the same structure may be linked, or different structures may be linked. When multiple aromatic heterocyclic groups are linked, typically a structure with 2 to 10 linked groups is common, and a structure with 2 to 5 linked groups is preferred. The substituents that these groups may have are the substituent group W. １ Selected from: <Aromatic Group> The aromatic group may have substituents and represents the aforementioned aromatic hydrocarbon group or aromatic heterocyclic group, and refers to a monovalent, divalent, or trivalent or more structure depending on the bonding state in the structure of the compound that is the subject of the description below. The aromatic group may be a group in which multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, the same structure may be linked, or different structures may be linked. When multiple aromatic hydrocarbon groups and / or aromatic heterocyclic groups are linked together, a structure in which 2 to 10 are linked together is usually given, and a structure in which 2 to 5 are linked together is preferred. The substituents that these groups may have are substituent group W １ Selected from.

[0070] <Amino Group> The amino group may have substituents, preferably a secondary amino group or a tertiary amino group, and more preferably a tertiary amino group. Preferred substituents on the amino group are groups selected from hydrocarbon group A, or aromatic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the amino group, they may be the same or different, and may be bonded to each other to form a ring with the nitrogen atom to which each is bonded. Specific examples include dimethylamino group, diethylamino group, ethylmethylamino group, n-propylmethylamino group, di-iso-propylamino group, di-n-butylamino group, di-n-hexylamino group, 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 substituent group W. １ Selected from.

[0071] <Halogen Atoms> Halogen atoms are typically fluorine, chlorine, bromine, or iodine atoms. More preferably, they are fluorine atoms.

[0072] <Alkyloxycarbonyl Group> The alkyloxycarbonyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 or more carbon atoms and 30 or less, more preferably 20 or less carbon atoms as the upper limit of the number of carbon atoms, and even more preferably 10 or less carbon atoms. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0073] <Alkylsulfonyl Group> Alkylsulfonyl groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 1 or more and 30 or less, more preferably 20 or less as the upper limit of the number of carbon atoms, and even more preferably 10 or less. Specific examples include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, dodecylsulfonyl group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0074] <Aralkyl Group> The aralkyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 20 carbon atoms or less. Specific examples include benzyl group, 2-phenylethyl group, 2-phenylpropyl-2-yl group, 2-phenylbutyl-2-yl group, 3-phenylpentyl-3-yl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, 7-phenyl-1-heptyl group, 8-phenyl-1-octyl group, etc. The substituents that these groups may have are substituted group W. １ Selected from.

[0075] <Boryl Group> The boryl group may have substituents, preferably a secondary boryl group or a tertiary boryl group, and more preferably a tertiary boryl group. Preferred substituents on the boryl group are hydroxyl groups, alkyloxycarbonyl groups, alkyl groups, cycloalkyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups, and these groups may also have substituents. Furthermore, if there are multiple substituents on the boryl group, they may be the same or different, and they may be bonded to each other, forming a ring with the boron atom to which each is bonded. The substituents that these groups may have are substituted group W. １ Selected from.

[0076] <Acyl Group> The acyl group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 2 to 50 carbon atoms, more preferably 24 carbon atoms or less as the upper limit of the carbon number, and even more preferably 12 carbon atoms or less. Specific examples include the benzoyl group and the acetyl group. The substituents that these groups may have are the substituent group W. １ Selected from.

[0077] <Aromatic Oxy Group> The aromatic oxy group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 3 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the carbon number, and even more preferably 20 carbon atoms or less. Specific examples include naphthoxy groups and phenyloxy groups. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0078] <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, 8-phenyl-1-octyloxy group, etc. The substituents that these groups may have are grouped W. １ Selected from.

[0079] <Aromatic Thio Group> The aromatic thio group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 3 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the carbon number, and even more preferably 20 carbon atoms or less. Specific examples include naphthylthio group, tolylthio group, phenylthio group, etc. The substituents that these groups may have are the substituent group W. １ Selected from.

[0080] <Aalkylthio group> The aralkylthio group may have substituents, and the number of carbon atoms is not usually limited, but preferably it has 4 to 50 carbon atoms, more preferably 30 carbon atoms or less as the upper limit of the number of carbon atoms, and even more preferably 20 carbon atoms or less. Specific examples include benzylthio group, tolylmethylthio group, 2-phenylethylthio group, 2-phenylpropyl-2-ylthio group, 2-phenylbutyl-2-ylthio group, 3-phenylpentyl-3-ylthio group, 3-phenyl-1-propylthio group, 4-phenyl-1-butylthio group, 5-phenyl-1-pentylthio group, 6-phenyl-1-hexylthio group, 7-phenyl-1-heptylthio group, 8-phenyl-1-octylthio group, etc. The substituents that these groups may have are grouped W. １ Selected from.

[0081] <Hydrogen Ring Group> A hydrocarbon ring group is a cyclic hydrocarbon group that may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 or more and 50 or less, more preferably 20 or less as the upper limit of the number of carbon atoms, and even more preferably 10 or less. Specific examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, or groups formed by linking multiple of these groups. The substituents that these groups may have are categorized as substituent group W. １ Selected from.

[0082] <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 groups can be listed.

[0083] Specific examples of unsubstituted hydrocarbon group A are hydrocarbon chains having 1 to 15 carbon atoms, more specifically, methyl group, ethyl group, 1-butyl group, tert-butyl group, cyclopentyl group, 4-ethyl-1-cyclohexyl group, 2-penten-1-yl group, 1-octyl group, 1-decyl group, etc., with methyl group, ethyl group, and 1-butyl group being preferred. Specific examples of hydrocarbon group A, in which part of the carbon chain is substituted with an oxygen atom, include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, dodecyloxy group, 2-ethoxyethyl group, 2-(2-ethoxyethoxy)ethyl group, 2-hydroxyethyl group, tetrahydropyranyloxypropyl group, and the like, with 2-ethoxyethyl group and 2-hydroxyethyl group being preferred, and 2-hydroxyethyl group being particularly preferred. Specific examples of hydrocarbon group A in which part of the carbon chain is substituted with a sulfur atom include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, tert-butylthio group, n-hexylthio group, cyclohexylthio group, dodecylthio group, 2-ethylthioethyl group, tetrahydrothienyl group, and 2-(2-ethylthioethylthio)ethyl group. Specific examples of cases where part of the carbon chain is substituted with an aromatic hydrocarbon group include benzyl group, phenylethyl group, phenylhexyl group, 4-phenylcyclohexylmethyl group, and 4-methylbenzyl group. Specific examples of hydrocarbon group A in which part of the carbon chain is substituted with a silicon atom include trimethylsilyl group, triethylsilyl group, propyldimethylsilyl group, tert-butyldimethylsilyl group, and tert-butyldiphenylsilyl group.Furthermore, a portion of the carbon chain may be simultaneously substituted with an oxygen atom 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, these groups are 2-(tert-butyldimethylsilyloxy)ethyl group, 4-(tert-butyldimethylsilyloxy)butyl group, and 2-(tert-butyldiphenylsilyloxy)ethyl group. Substituents that these groups may have are substituent group W. １ Selected from.

[0084] <Heterocyclic Groups> Heterocyclic groups may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 3 or more and 50 or less, more preferably 20 or less as the upper limit of the number of carbon atoms, and even more preferably 10 or less. Specific examples include thiane group, 1,4-dithiane group, tetrahydrofuran group, tetrahydropyran group, pyran group, 1,4-dioxane group, or groups formed by linking multiple of these groups. The substituents that these groups may have are the substituent group W １ Selected from.

[0085] <π-conjugated linkage group> A π-conjugated linkage group is a divalent group in the structure of a compound described below, consisting of alternating single and multiple bonds and possessing delocalized electrons (π electrons). A π-conjugated linkage group may have substituents, and the number of carbon atoms is not usually limited, but preferably it is 2 to 50 carbon atoms, more preferably 30 carbon atoms or less, and even more preferably 20 carbon atoms or less. Furthermore, substituents on multiple π-conjugated linkage groups may bond together to form a cyclic structure. Specific examples include divalent groups consisting of vinylene groups, phenylene groups, thiophene rings, furan rings, or pyrrole rings, or groups formed by linking multiple such groups. The substituents that these groups may have are categorized as substituent group W. １Selected from.

[0086] <Nonlinear Optical Materials> In this specification, "nonlinear optical materials" refers to nonlinear optically active compounds, nonlinear optically active polymer compounds, or both.

[0087] <Nonlinear Optically Active Compounds> In this specification, a nonlinear optically active compound refers to a compound with a molecular weight of less than 2000 that exhibits nonlinear optical activity. Nonlinear optically active compounds include compounds represented by formula (2).

[0088] <Nonlinear Optically Active Polymer Compounds> In this specification, a nonlinear optically active polymer compound refers to a polymer compound that exhibits nonlinear optical activity, and nonlinear optically active polymer compounds include polymer compounds containing repeating units represented by formula (1). When referring to a polymer compound containing repeating units represented by formula (1) with particular attention to its nonlinear optical activity, it shall be referred to as a nonlinear optically active polymer compound containing repeating units represented by formula (1). Furthermore, in this specification, a polymer compound that does not contain repeating units represented by formula (1) among nonlinear optically active polymer compounds shall be referred to as a nonlinear optically active polymer compound without repeating units represented by formula (1).

[0089] In this specification, the solids of a composition refer to the components other than the solvent contained in the composition, and even if the components other than the solvent are liquid at room temperature, they are included in the solids.

[0090] <Polymer compound containing repeating units represented by formula (1)> The polymer compound in this embodiment contains repeating units represented by formula (1). The polymer compound in this embodiment is bonded to a group obtained by removing one hydrogen atom from the compound represented by formula (2) below via a phenol group. Compared to cases where bonds are mediated by active groups such as ester bonds or urethane bonds containing carbonyl groups, it tends to be more robust against hydrolysis, has higher heat resistance, and can maintain nonlinear optical properties.

[0091]

[0092] [In formula (1), A １１A represents a trivalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A, which may have substituents, a trivalent aromatic group which may have substituents, a trivalent heterocyclic group which may have substituents, or a trivalent amino group which may have substituents. １２ and A １３ Each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, a carbonyl group, or an oxygen atom, R １１ Each of these is independently a group selected from hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, n １２ If the number is 2 or more, the R １１ is another R １１ It may also be bonded to form a ring, L １１ Each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, X １１ Each of these is independently a group obtained by removing one hydrogen atom from the compound represented by the following formula (2), n １１ n is an integer between 1 and 5. １２ n is an integer between 0 and 4. １３ n is an integer between 0 and 5. １４ and n １５ Each of these is an integer between 0 and 5, where n is independent. １１ to n １２ The sum of the numbers is 5 or less.

[0093] [A １１ ] A １１This refers to a trivalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A, which may have substituents; a trivalent aromatic group, which may have substituents; a trivalent heterocyclic group, which may have substituents; or a trivalent amino group, which may have substituents. A trivalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A, which may have substituents, is synonymous with the description given in the explanation of the terms above. A trivalent aromatic group, which may have substituents, is synonymous with the description given in the explanation of the terms above. A trivalent heterocyclic group, which may have substituents, is synonymous with the description given in the explanation of the terms above. A trivalent amino group, which may have substituents, is synonymous with the description given in the explanation of the terms above.

[0094] [A １２ A １３ ] A １２ and A １３ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, a divalent aromatic group which may have substituents, or a divalent heterocyclic group, carbonyl group, or oxygen atom which may have substituents. A divalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A, which may have substituents, is synonymous with the description given in the explanation of the terms above. A divalent aromatic group which may have substituents is synonymous with the description given in the explanation of the terms above. A divalent heterocyclic group which may have substituents is synonymous with the description given in the explanation of the terms above.

[0095] [R １１ ] R １１ Each of these is independently a group selected from hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, n １２ If the number is 2 or more, the R １１ is another R １１ It may bond with to form a ring. A group selected from hydrocarbon group A, which may have substituents, is described in the same way as described in the explanation of the terms above. Aromatic groups, which may have substituents, are described in the same way as described in the explanation of the terms above. R １１For the film, substituted hydrocarbon chain groups, which may have substituents, and phenyl groups are preferred due to film stability, substituted hydrocarbon chain groups with 1 to 20 carbon atoms and phenyl groups are more preferred, methyl groups, methoxy groups, and phenyl groups are particularly preferred, and methyl groups are most preferred.

[0096] [L １１ ] L １１ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents. A divalent group obtained by removing two hydrogen atoms from a group selected from hydrocarbon group A, which may have substituents, is synonymous with the description given in the explanation of the terms above. A divalent aromatic group which may have substituents is synonymous with the description given in the explanation of the terms above. A divalent heterocyclic group which may have substituents is synonymous with the description given in the explanation of the terms above. From the viewpoint of the durability of the compound, a carbonyl group, an oxygen atom, or a divalent aromatic group which may have substituents is preferred, and a divalent aromatic group which may have substituents is preferred.

[0097] [X １１ ] X １１ Each of these groups is independently a group obtained by removing one hydrogen atom from the compound represented by the following formula (2).

[0098] [n １１ ] n １１ n is an integer from 1 to 5. From the standpoint of compound stability, １１ 1 is preferable.

[0099] [n １２ ] n １２ n is an integer between 0 and 4. １１ to n １２ The sum of is 5 or less. From the standpoint of the stability of the compound, n １２ 0 or 1 is preferred.

[0100] [n １３ ] n １３ n is an integer between 0 and 5. From the standpoint of compound stability, １３ The value is preferably 0 to 2, and more preferably 0.

[0101] [n １４ , n １５ ] n １４ and n １５ Each of these is an integer from 0 to 5, independently of the others. From the standpoint of the stability of the compound, n １４ and n １５ The value is preferably 0 to 2.

[0102] [Substituents] These A １１ ~A １３ , L １１ and R １１ Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group described in the above-mentioned explanations, and are preferably groups selected from the substituent group W1.

[0103] <Formula (2)>

[0104]

[0105] [In formula (2), Ar ２１ Each of these is independently a divalent aromatic group which may have substituents, and R ２１ and R ２３ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, or a divalent aromatic group which may have substituents, and R ２２ and R ２４ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ２１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ２１ This is a group represented by the following formula (3), and m ２１ Each of these is an integer between 0 and 5, and m ２２ m is an integer between 1 and 5. ２３ n is an integer between 0 and 5. ２１ [This is an integer between 1 and 15.]

[0106] [Ar ２１ ] Ar ２１These are, independently, divalent aromatic groups which may have substituents. The term "divalent aromatic group which may have substituents" is synonymous with the description given in the previous explanation of the terms. Ar ２１ The group is preferably a divalent group consisting of a benzene ring, a naphthalene ring, a 9,9-dialkylfluorene ring, a thiophene ring, or a biphenyl ring, and more preferably a divalent group consisting of a benzene ring, and these groups may have substituents.

[0107] [R ２１ , R ２３ ] R ２１ and R ２３ Each is independently a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, or a divalent aromatic group, which may have substituents. A divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, is synonymous with the description given in the explanation of the terms above. A divalent aromatic group, which may have substituents, is synonymous with the description given in the explanation of the terms above. From the viewpoint of film formation, R ２１ and R ２３ Preferably, R is a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have a benzene ring, a naphthalene ring, or substituents having 10 or fewer carbon atoms, and more preferably, a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have a benzene ring, or substituents having 5 or fewer carbon atoms. Also, from the viewpoint of solubility, ２１ and R ２３ They may be the same or different, but it is preferable that they be different.

[0108] [R ２２ , R ２４ ] R ２２ and R ２４Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom. A group selected from hydrocarbon group A which may have substituents is synonymous with the description given in the explanation of the terms above. An aromatic group which may have substituents is synonymous with the description given in the explanation of the terms above. An amino group which may have substituents is synonymous with the description given in the explanation of the terms above. A halogen atom is synonymous with the description given in the explanation of the terms above. From the viewpoint of improving nonlinear optical properties, R ２２ and R ２４ The group is preferably a group selected from hydrocarbon group A, which may have substituents, or an amino group, more preferably a group selected from hydrocarbon group A having 1 to 20 carbon atoms, which may have substituents, or an amino group, and is particularly preferably a linear alkyl group having 1 to 5 carbon atoms, which may be substituted, an ethoxy group, or an tertiary amino group, which may be substituted.

[0109] [Y ２１ ] Y ２１ Each of these is independently a divalent π-conjugated linkage group which may have substituents. ２１ If there are multiple Y ２１ The structures may be the same or different. Also, Y ２１ Multiple substituents on the compound may form bonds to create a cyclic structure. The term π-conjugated linkage is synonymous with the description given in the explanation of the terms above.

[0110] [Z ２１ ] Z ２１ This is the base represented by equation (3) described later.

[0111] [Substituents] These Ar ２１ , R ２１ ~R ２４ and Y ２１ Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group as described in the explanations of the terms above.

[0112] [subscript m ２１ , m２２ , m ２３ , n ２１ ] m ２１ Each of these is an integer between 0 and 5, and m ２２ m is an integer between 1 and 5. ２３ n is an integer between 0 and 5. ２１ m is an integer between 1 and 15. From the viewpoint of improving the nonlinear optical properties of the dye, ２１ m is preferably an integer between 0 and 4, more preferably an integer between 0 and 3, and even more preferably an integer between 0 and 2. ２２ m is preferably an integer between 1 and 4, and more preferably an integer between 1 and 3. ２３ n is preferably an integer between 0 and 4, more preferably an integer between 0 and 3, and even more preferably an integer between 0 and 2. ２１ Preferably, it is 1 or more, more preferably 2 or more, even more preferably 3 or more, and from the viewpoint of reducing absorption loss, it is preferably 14 or less, more preferably 13 or less, and even more preferably 10 or less.

[0113] <Formula (3)>

[0114]

[0115] [In formula (3), *J ３１ Y ２１ This represents the bonding position with R ３１ and R ３２ Each independently represents a group selected from hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, and R ３１ and R ３２ They may be bonded together to form a ring, or R ３１ and R ３２ R ３１ and R ３２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ３３ ~R ３５ Each independently represents a cyano group, a C2-C30 alkyloxycarbonyl group which may have substituents, or a C1-C30 alkylsulfonyl group which may have substituents, X ３１ is an oxygen atom, a sulfur atom, or N-Q３１ This represents Q ３１ This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents.

[0116] [*J ３１ ] *J ３１ Y ２１ This indicates the connection point with [the other element].

[0117] [R ３１ , R ３２ ] R ３１ and R ３２ Each independently represents a group selected from hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, and R ３１ and R ３２ They may be bonded together to form a ring, or R ３１ and R ３２ R ３１ and R ３２ These may form a carbonyl group together with the carbon atom to which they are bonded. Groups selected from hydrocarbon group A, which may have substituents, are described in the same way as described in the explanation of the terms above. Aromatic groups, which may have substituents, are described in the same way as described in the explanation of the terms above. From the viewpoint of film formation, R ３１ and R ３２ The R is preferably a group selected from group A of hydrocarbon groups with 1 to 20 carbon atoms, which may have substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may be substituted, with methyl, ethyl, linear or branched propyl, phenyl, and naphthyl groups being particularly preferred, and methyl and phenyl groups being the most preferred. ３１ and R ３２ The substituents that may be present are the substituent group W. １ It is preferable that the atoms be selected from among alkyl groups and halogen atoms, more preferably a fluorine atom, and most preferably a fluorine atom.

[0118] [R ３３ ~R ３５ ] R ３３ ~R ３５Each of these independently represents a cyano group, an alkyloxycarbonyl group having 2 to 30 carbon atoms that may have substituents, or an alkylsulfonyl group having 1 to 30 carbon atoms that may have substituents. The alkyloxycarbonyl group having 2 to 30 carbon atoms that may have substituents is synonymous with the description given in the explanation of the terms above. The alkylsulfonyl group having 1 to 30 carbon atoms that may have substituents is synonymous with the description given in the explanation of the terms above. From the viewpoint of improving nonlinear optical properties, R ３３ ~R ３５ The group is preferably a cyano group, a C2-C10 alkyloxycarbonyl group which may have substituents, or a C1-C10 alkylsulfonyl group which may have substituents, with a cyano group being more preferred.

[0119] [X ３１ ] X ３１ is an oxygen atom, a sulfur atom, or N-Q ３１ It represents.

[0120] [Q ３１ ] Q ３１ This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. A group selected from hydrocarbon group A which may have substituents is synonymous with the description given in the explanation of the terms above. An aralkyl group which may have substituents is synonymous with the description given in the explanation of the terms above. From the viewpoint of film formation, a group selected from hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents is preferred, an aralkyl group which may have substituents is more preferred, and an aralkyl group which may have substituents is particularly preferred.

[0121] [Substituents] These R ３１ ~R ３５ and Q ３１ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the explanation of the terms above, and preferably the substituent group W １ It is a base selected from among them.

[0122] <Preferred form 1 of formula (2)> Y in formula (2)２１ Preferably, at least one of them is independently represented by formula (4), provided that n in formula (2) ２１ If it is 2 or more, Y ２１ R inside ４１ and R ４２ is, other Y ２１ R included ４１ or R ４２ They may be connected to form a ring. When they are connected to form a ring, R ４１ and R ４２ Either of them may be a single bond.

[0123] <Formula (4)>

[0124]

[0125] [In formula (4), R ４１ and R ４２ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ４１ and R ４２ They may be joined together to form a ring.

[0126] [R ４１ , R ４２ ] R ４１ and R ４２ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group. A group selected from hydrocarbon group A which may have substituents is synonymous with the description given in the explanation of the terms above. An aromatic group which may have substituents is synonymous with the description given in the explanation of the terms above. An amino group which may have substituents is synonymous with the description given in the explanation of the terms above. A halogen atom is synonymous with the description given in the explanation of the terms above. A optionally substituted boryl group is synonymous with the description given in the explanation of the terms above. Also, R ４１and R ４２ They may be bonded together to form a ring. ４１ and R ４２ When R is bonded to form a ring, ４１ and R ４２ Any of them may be a single bond. ４１ and R ４２ The relationship can be either a cis-field or a trans-field.

[0127] [Substituents] These R ４１ and R ４２ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the explanation of the terms above, and preferably the substituent group W １ It is a base selected from among them.

[0128] <Preferred form 2 of formula (2)> Y in formula (2) ２１ Preferably, at least one of these is independently represented by the following formula (5), formula (6), or formula (7), provided that n in formula (2) ２１ If it is 2 or more, Y ２１ R inside ５１ , R ５２ , R ６１ , R ６２ , and R ７１ ~R ７７ is, other Y ２１ R included ５１ , R ５２ , R ６１ , R ６２ , or R ７１ ~R ７７ They may be connected to form a ring. When they are connected to form a ring, R ５１ , R ５２ , R ６１ , R ６２ and R ７１ ~R ７７ Either of them may be a single bond.

[0129] <Formula (5)>

[0130]

[0131] [In formula (5), R ５１ and R ５２Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ５１ and R ５２ They may be joined together to form a ring.

[0132] [R ５１ , R ５２ ] R ５１ and R ５２ R in equation (4) ４１ and R ４２ This is synonymous with R. From the viewpoint of improving the nonlinear optical effect, preferably R ５１ , R ５２ is a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[0133] <Formula (6)>

[0134]

[0135] [In formula (6), R ６１ and R ６２ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ６１ and R ６２ They may be joined together to form a ring, X ６１ is an oxygen atom, a sulfur atom, or N-Q ６１ This represents Q ６１ This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or an optionally substituted boryl group.

[0136] [R ６１ , R ６２ ] R６１ and R ６２ R in equation (4) ４１ and R ４２ This is synonymous with R. From the viewpoint of improving the nonlinear optical effect, preferably R ６１ , R ６２ is a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, more preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom.

[0137] [X ６１ ] X ６１ is an oxygen atom, a sulfur atom, or N-Q ６１ This represents a sulfur atom, preferably, from the viewpoint of improving nonlinear optical effects.

[0138] [Q ６１ ] Q ６１ This represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or an aromatic group which may have substituents. A group selected from hydrocarbon group A which may have substituents is synonymous with the description given in the explanation of the terms above. An aromatic group which may have substituents is synonymous with the description given in the explanation of the terms above. From the viewpoint of film formation, a group selected from hydrocarbon group A with 1 to 20 carbon atoms which may have substituents, and an aromatic hydrocarbon group having 6 to 60 carbon atoms are preferred, a group selected from hydrocarbon group A with 1 to 20 carbon atoms which may have substituents, and an aromatic hydrocarbon group having 6 to 30 carbon atoms are more preferred, and a group selected from hydrocarbon group A with 1 to 10 carbon atoms which may have substituents, and an aromatic hydrocarbon group having 6 to 20 carbon atoms are particularly preferred.

[0139] [Substituent] Q ６１ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the explanation of the terms above, and preferably the substituent group W １ It is a base selected from among them.

[0140] <Formula (7)>

[0141]

[0142] [In formula (7), R ７１ ~R ７７ Each independently represents a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, an aromatic group which may have substituents, a hydroxyl group, an amino group which may have substituents, a thiol group, a cyano group, a halogen atom, or a boryl group which may have substituents, and R ７１ ~R ７７ At least two of them may be joined together to form a ring.

[0143] [R ７１ ~R ７７ ] R ７１ ~R ７７ R in equation (4) ４１ and R ４２ It is synonymous with R. ７１ ~R ７７ At least two of them may be bonded together to form a ring. From the viewpoint of improving the nonlinear optical effect, preferably R ７１ R is a hydrogen atom, a group selected from hydrocarbon group A which may have substituents, or an aromatic group which may have substituents. ７２ ~R ７７ is a hydrogen atom, may have substituents, or is a group selected from hydrocarbon group A. More preferably, R ７１ R is a hydrogen atom or a group selected from hydrocarbon group A, which may have a substituent, ７２ , R ７３ , R ７６ , R ７７ is a hydrogen atom, and R ７４ , R ７５ is a hydrogen atom or a group selected from hydrocarbon group A, which may have a substituent. Most preferably, R ７１ R is a hydrogen atom or a group selected from hydrocarbon group A, which may have a substituent, ７２ , R ７３ , R ７６ , R ７７ is a hydrogen atom, and R ７４ , R ７５ is a hydrogen atom or an alkyl group.

[0144] [Substituents] These R ７２ ~R ７７ Unless otherwise specified, the substituents that may be present are the same as the substituents that may be present on each group described in the explanation of the terms above, and preferably the substituent group W １ It is a base selected from among them.

[0145] <Preferred form of formula (1)> A of formula (1) １１ However, it is preferable that each be represented independently by the following formula (8) or formula (9).

[0146] <Formula (8)>

[0147]

[0148] [In formula (8), R ８１ ~R ８３ Each of these independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom. *J ８１ is, L １１ This indicates the connection point with [the other element].

[0149] [R ８１ ~R ８３ ] R ８１ ~R ８３ Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have substituents, or a halogen atom.

[0150] Specific examples of linear alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, n-butyl, and n-pentyl groups.

[0151] Specific examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms. From the viewpoint of improving nonlinear optical effects, fluorine atoms or chlorine atoms are preferred, and fluorine atoms are more preferred.

[0152] From the standpoint of compound stability, R ８１ ~R ８３ A hydrogen atom or a methyl group is preferred.

[0153] [Substituent] R ８１ ~R ８３The substituents that the linear alkyl group having 1 to 5 carbon atoms may have are preferably halogen atoms, more preferably fluorine atoms, or chlorine atoms, and even more preferably fluorine atoms, from the viewpoint of the durability of the compound.

[0154] [*J ８１ ] *J ８１ is, L １１ This indicates the connection point with [the other element].

[0155] <Formula (9)>

[0156]

[0157] [In formula (9), R ９１ and R ９２ Each of these independently represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, which may have substituents. *J ９１ is, L １１ This indicates the connection point with [the other element].

[0158] [R ９１ , R ９２ ] R ９１ and R ９２ Each of these independently represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, which may have substituents.

[0159] Specific examples of linear alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, n-butyl, and n-pentyl groups.

[0160] [Substituent] R ９１ and R ９２ The substituents that the linear alkyl group having 1 to 5 carbon atoms may have are preferably halogen atoms, more preferably fluorine atoms, or chlorine atoms, and even more preferably fluorine atoms, from the viewpoint of the durability of the compound.

[0161] From the standpoint of the durability of the compound, R ９１ and R ９２ Preferably, it is a hydrogen atom.

[0162] [*J ９１ ] *J ９１ is, L １１ This indicates the connection point with [the other element].

[0163] A in formula (1) above １２ and A １３ However, it is preferable that each be represented independently by the following formula (8) or formula (9).

[0164] <Further Repeating Units> The polymer compound according to the embodiment of the present invention may further contain repeating units other than those described above. There are no particular restrictions on the further repeating units that may be included, but for example, repeating units represented by the following formula (11) can be listed.

[0165] <Formula (11)> The polymer compound according to the embodiment of the present invention may further contain a repeating unit represented by the following formula (11).

[0166]

[0167] [In formula (11), R １１１ ~R １１６ Each of these is independently a group selected from the hydrocarbon group A, which may have a hydrogen atom or a substituent, and L １１１ and L １１２ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents, Y １１１ and Y １１２ Each of these is independently a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, a hydroxyl group which may have substituents, or a silyl group which may have substituents, and R １１３ ~R １１６ , L １１１ and L １１２ At least two of them may be joined together to form a ring, n １１１ and n １１２ Each of these is an integer between 0 and 5, independently of the others.

[0168] [R １１１ ~R １１６ ] R １１１ ~R １１６Each of these independently represents a hydrogen atom or a group selected from the hydrocarbon group A, which may have substituents. The group selected from the hydrocarbon group A, which may have substituents, is synonymous with the description given in the explanation of the terms above. From the standpoint of the stability of the compound, R １１１ and R １１２ A hydrogen atom is preferred, R １１３ ~R １１６ Preferably, the group consists of a hydrogen atom and an alkyl group as described in the explanation of the terms above, more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, and an ethyl group.

[0169] [L １１１ , L １１２ ] L １１１ and L １１２ Each of these independently represents a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, an oxygen atom, a carbonyl group, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents. A group selected from hydrocarbon group A which may have substituents, a divalent aromatic group which may have substituents, or a divalent heterocyclic group which may have substituents is synonymous with the description given in the explanation of the terms above. From the standpoint of the stability of the compound, L １１１ and L １１２ Preferably, R is a divalent group obtained by removing one hydrogen atom from a group selected from hydrocarbon group A, which may have substituents, an oxygen atom, or a carbonyl group. １１３ ~R １１６ , L １１１ and L １１２ At least two of them may be joined together to form a ring.

[0170] [Y １１１ , Y １１２ ] Y １１１ and Y １１２Each of these independently represents a hydrogen atom, a group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, a hydroxyl group which may have substituents, or a silyl group which may have substituents. A group selected from the hydrocarbon group A which may have substituents, an aromatic group which may have substituents, or a heterocyclic group which may have substituents, a hydroxyl group which may have substituents, or a silyl group which may have substituents is synonymous with the description given in the explanation of the terms above. From the standpoint of the stability of the compound, Y １１１ and Y １１２ The hydrogen atom is preferably a group selected from hydrocarbon group A, which may have substituents, or an aromatic group, which may have substituents; more preferably a hydrogen atom or a group selected from hydrocarbon group A, which may have substituents; and a hydrogen atom is particularly preferred.

[0171] [n １１１ , n １１２ ] n １１１ and n １１２ Each of these is an integer from 0 to 5, independently of the others. From the standpoint of the stability of the compound, n １１１ and n １１２ The integer is preferably between 0 and 2.

[0172] [Substituents] These R １１１ ~R １１６ , L １１１ , L １１２ , Y １１１ and Y １１２ Unless otherwise specified, the substituents that may be present are synonymous with the substituents that may be present on each group described in the above-mentioned explanations, and are preferably groups selected from the substituent group W1.

[0173] <Example Structure of Repeating Unit Represented by Formula (1)> Below are specific examples of repeating units represented by formula (1) that are included in the polymer compound in this embodiment. The present invention is not limited to these.

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184] <Exemplary Structures of the Compound Represented by Formula (2)> As the compound represented by formula (2), for example, compounds represented by formula (2)-1 to formula (2)-210 can be mentioned, but are not limited thereto. Further, these compounds may further have substituents.

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208] <Exemplary structures of the group represented by formula (3)> As the group represented by formula (3), for example, groups represented by formula (3)-1 to formula (3)-31 can be mentioned, but it is not limited thereto. Further, these groups may further have substituents.

[0209]

[0210]

[0211] <Optional repeating unit> The polymer compound in the present embodiment may contain a repeating unit (R) in addition to the repeating unit represented by formula (1). Here, the repeating unit (R) does not include the repeating unit represented by formula (1), and for example, the repeating unit represented by the above formula (11) is included. By containing a repeating unit different from the repeating unit represented by formula (1), the durability of the polymer compound is improved.

[0212] The repeating unit (R) is not particularly limited, but examples include poly(meth)acrylic acid esters (e.g., polymethyl methacrylate (PMMA), polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), polycarbonylaminoethyl methacrylate, etc.), polyamide, polyimide, polycarbonate, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyester, polyolefin, polyphenylene sulfide, aromatic polyamine, polyamine, polyurea, silicone resin, epoxy resin, polyvinyl chloride, and repeating units constituting fluoropolymers.

[0213] 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.

[0214] The following are specific examples of repeating units (R) in this embodiment. The present invention is not limited to these examples.

[0215]

[0216]

[0217]

[0218]

[0219] <Examples of Preferred Polymer Compounds> The following are preferred specific examples of polymer compounds in this embodiment. The present invention is not limited to these. PA represents a repeating unit represented by formula (1), and PB and PC represent repeating units (R).

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230] <Substituted Phenol Repeating Units> The polymer compound according to this embodiment may have a substituted phenol repeating unit (C-1) as a repeating unit different from the repeating unit and repeating unit (R) represented by formula (1). The usefulness of the substituted phenol repeating unit (C-1) is that by modifying the phenol residue after dye introduction, durability, solubility and / or substrate adhesion can be improved. Groups that can modify the phenol residue include the hydrocarbon group A described in the explanation of the terms above, alkylcarbonyl groups having 1 to 10 carbon atoms, and silyl groups described in the explanation of the terms above. From the viewpoint of compound stability, hydrocarbon group A is preferred, more preferably hydrocarbon group A having 1 to 10 carbon atoms, and particularly preferably hydrocarbon group A having 1 to 6 carbon atoms. The substituted phenol repeating unit (C-1) may be introduced using the phenol residue after dye introduction, or it may be introduced by adding a monomer separately.

[0231] <Crosslinking Group> The polymer compound according to this embodiment may have a crosslinking group. Having a crosslinking group allows for crosslinking after poling treatment, improving the durability of the compound. Examples of crosslinking groups include vinyl group, acryloyl group, methacryloyl group, allyl group, thiol group, polyamine, polyol, isocyanate group, cyanoacryloyl group, cinnamyl group, cinnamoyl group, cinnamyridene group, cinnamyridene acetyl group, α-methylcinnamyridene group, α-methylcinnamyridene acetyl group, α,γ-dimethylcinnamyridene group, α,γ-dimethylcinnamyridene acetyl group, α-phenylcinnamyridene group, α-phenylcinnamyridene acetyl group, α-phenoxycinnamyridene group, α-phenoxycinnamyridene acetyl group, α-cyanocinnamyridene group, α-cyanocinnamyridene acetyl group, chalcone residue, oxetane group, epoxy group, isocoumarin residue, 2,5-dimethoxystilbene residue, thymine residue, stilpyridinium residue, maleimide residue, α-phenylmaleimide residue, anthracene residue, 2-pyridinium Examples include ron residues, vinyl ether groups, trifluorovinyl ether groups, benzocyclobutene groups, 1-phenyloxybenzocyclobutene groups, and their derivatives. Preferably, examples include acryloyl groups, methacryloyl groups, thiol groups, isocyanate groups, blocked isocyanate groups, cinnamoyl groups, cinnamyridene groups, α-cyanocinnamyridene groups, anthracene residues, maleimide residues, benzocyclobutene groups, and 1-phenyloxybenzocyclobutene groups. More preferably, examples include acryloyl groups, thiol groups, isocyanate groups, blocked isocyanate groups, anthracene residues, maleimide residues, benzocyclobutene groups, and 1-phenyloxybenzocyclobutene groups. Particularly preferred are acryloyl groups, isocyanate groups, blocked isocyanate groups, anthracene residues, maleimide residues, and 1-phenyloxybenzocyclobutene groups.

[0232] The polymer compound according to this embodiment may have repeating units containing crosslinking groups. Having repeating units containing crosslinking groups allows for crosslinking after poling treatment, improving the durability of the compound. Examples of crosslinking groups include the crosslinking groups described above, and preferred crosslinking groups are also as described above.

[0233] <Examples of repeating units containing crosslinking groups> The following are preferred specific examples of repeating units (CL) containing crosslinking groups. The present invention is not limited to these.

[0234]

[0235] The polymer compound according to this embodiment may also contain, in addition to the repeating unit represented by formula (1), a repeating unit having a side chain that is obtained by removing one hydrogen atom from the compound represented by formula (2), as long as the effects of the present invention are not impaired.

[0236] <Examples of Polymer Compounds> The following are preferred specific examples of polymer compounds in this embodiment. The present invention is not limited to these. PA represents a repeating unit represented by formula (1), and PCL represents a repeating unit (CL).

[0237]

[0238] When expressing the content of the repeating unit represented by formula (1) in the polymer compound according to this embodiment as a mole percentage, there are no particular restrictions on the mole percentage of the repeating unit represented by formula (1) relative to the total of each repeating unit in the polymer compound of this embodiment. However, from the viewpoint of balancing electro-optic effect and solubility, the lower limit is preferably 0.1 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more. The upper limit is preferably 80 mol% or less, more preferably 60 mol% or less, even more preferably 40 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less.

[0239] When expressing the content of the repeating units represented by formula (1) in the polymer compound according to this embodiment as a mole percentage, there are no particular restrictions on the mole percentage of the groups derived from the nonlinear optical compound relative to the total of each repeating unit of the polymer compound according to this embodiment. However, from the viewpoint of balancing electro-optical effects 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.

[0240] When expressing the content of the repeating unit represented by formula (1) in the polymer compound according to this embodiment as a mass ratio, there are no particular restrictions on the content of the group derived from the compound represented by formula (1) in the polymer compound according to this embodiment. However, from the viewpoint of balancing electro-optic effect and solubility, when the total mass of the polymer compound according to this embodiment is 100, the lower limit is preferably 1 or more, more preferably 10 or more, even more preferably 20 or more, and the upper limit is preferably 80 or less, more preferably 60 or less, and even more preferably 50 or less.

[0241] The weight-average molecular weight of the polymer compound according to this embodiment is not particularly limited, but is preferably 0.5 million or more, more preferably 10,000 or more, and even more preferably 30,000 or more, as this improves durability. Furthermore, for solubility, it is preferably 500,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less, and particularly preferably 100,000 or less. The weight-average molecular weight of the polymer compound according to this embodiment is confirmed by measuring the weight-average molecular weight of polystyrene as a standard using GPC.

[0242] There are no particular restrictions on the molecular weight distribution of the polymer compound according to this embodiment, but it is preferably 5 or less, more preferably 3 or less, and even more preferably 2.5 or less. From the viewpoint of performance improvement, it is preferable that the molecular weight distribution of the polymer compound according to this embodiment is 3 or less. The molecular weight distribution of the polymer compound according to this embodiment is confirmed by measuring the ratio of the number average molecular weight to the weight average molecular weight when polystyrene is used as a standard by GPC.

[0243] There are no particular limitations on the glass transition temperature (Tg) of the polymer compound according to this embodiment, but it is generally between 40°C and 300°C. A temperature of 45°C or higher is preferred, 50°C or higher is more preferred, and 80°C or higher is even more preferred, as this improves heat resistance. Furthermore, from the viewpoint of the polling process, a temperature of 280°C or lower is preferred, 230°C or lower is more preferred, 200°C or lower is even more preferred, and 180°C or lower is even more preferred. The Tg of the polymer compound according to this embodiment is confirmed by measuring the temperature corresponding to the intersection of the gradient of the endothermic rising portion of the baseline shift of the DSC curve associated with the glass transition and the baseline using a differential scanning calorimeter (DSC).

[0244] There are no particular restrictions on the decomposition temperature (Td) of the polymer compound according to this embodiment, but it is preferably 0°C or higher, more preferably 40°C or higher, and even more preferably 80°C or higher. The Td of the polymer compound according to this embodiment can be confirmed by measuring the temperature at which the mass decreases by 5% using a thermogravimetric differential thermal analyzer (TG-DTA).

[0245] <Composition> The composition according to the embodiment of the present invention comprises at least a polymer compound according to the embodiment of the present invention and an organic solvent. The composition may also contain polymer materials, nonlinear optically active compounds, and other components.

[0246] Examples of nonlinear optically active materials and solvents contained in the composition include the following combinations. - Nonlinear optically active polymer compound containing a repeating unit represented by formula (1) / solvent - Nonlinear optically active polymer compound containing a repeating unit represented by formula (1) / solvent - Nonlinear optically active polymer compound containing a repeating unit represented by formula (1) / polymer material / solvent - Nonlinear optically active polymer compound containing a repeating unit represented by formula (1) / nonlinear optically active polymer compound without a repeating unit represented by formula (1) / solvent - Nonlinear optically active polymer compound containing a repeating unit represented by formula (1) / nonlinear optically active polymer compound without a repeating unit represented by formula (1) / solvent - Nonlinear optically active polymer compound containing a repeating unit represented by formula (1) / nonlinear optically active polymer compound without a repeating unit represented by formula (1) / polymer material / solvent Note that the above nonlinear optically active compound, nonlinear optically active polymer compound containing a repeating unit represented by formula (1), nonlinear optically active polymer compound without a repeating unit represented by formula (1), polymer material, and solvent may each be included in the composition in quantities of two or more.

[0247] [Organic solvent] From the viewpoint of improving the processability of the composition, it is preferable that the composition according to the embodiment of the present invention contains an organic solvent. The organic solvent that can be used in the composition is not particularly limited as long as it dissolves the polymer compound containing the repeating unit represented by the above formula (1), but for example, aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, styrene; aliphatic hydrocarbons such as n-hexane, n-heptane; halogenated hydrocarbons such as chlorobenzene, orthodichlorobenzene, chloroform, dichloromethane, dibromomethane, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxybenzotrifluoride, 3-methoxybenzotrifluoride; ketones such as acetone, ethyl methyl ketone, isopropyl methyl ketone, isobutyl methyl ketone, butyl methyl ketone, diacetone alcohol, diethyl ketone, cyclopentanone, cyclohexanone; ethyl acetate, propyl acetate, phenyl acetate, 2-methoxyethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethyl acetate, γ-butyrolamine Esters such as ethyl benzoate, methyl benzoate, benzoyl benzoate, 2-ethylhexyl benzoate, and ethyl 4-methylbenzoate; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone; alcohols such as methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, isobutyl alcohol, tert-butyl alcohol, pentanol, 2-methylbutanol, 2-methyl-2-butanol, cyclohexanol, 2-methylpentanol, octanol, 2-ethylhexanol, benzyl alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; glycols such as ethylene glycol, propylene glycol, hexylene glycol, trimethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol;Examples include ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide, anisole, etc. These organic solvents may be used individually or in combination of two or more.

[0248] Of the above organic solvents, chlorobenzene, orthodichlorobenzene, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxybenzotrifluoride, 3-methoxybenzotrifluoride, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are more preferred from the viewpoint of applicability, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are even more preferred, and cyclopentanone, cyclohexanone, toluene, anisole, and dibromomethane are particularly preferred.

[0249] [Polymer material] From the viewpoint of improving the heat resistance of the composition, it is preferable that the composition according to the embodiment of the present invention includes a polymer material. As for the polymer material, there are no particular restrictions as long as it is a polymer compound that can disperse a nonlinear optical material, but a transparent polymer that does not scatter is preferred for use as an optical material. Examples include (meth)acrylate polymers (e.g., polymethyl methacrylate (PMMA)), polyamides, polyimides, polycarbonates, polydicyclopentanyl methacrylate (poly DCPMA), polyadamantyl methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), etc.), cycloolefin polymers, cycloolefin copolymers, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyester, polyolefin, polyphenylene sulfide, polyurea, silicone resins, epoxy resins, polyvinyl chloride, fluororesins, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, and copolymers thereof. Of these, at least one selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl chloride, polystyrene, polyimide, polycarbonate, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, and polymers thereof is preferred from the viewpoint of molecular orientation. Furthermore, methyl poly(meth)acrylate is preferred as the poly(meth)acrylic acid ester. The above organic polymers may be used individually or in combination of multiple types. In this specification, the polymer material can also be said to be a polymer compound that does not have nonlinear optical activity.

[0250] [Other Components] The compositions according to the embodiments of the present invention may contain other components not listed above. There are no particular limitations on the components that the composition may further contain, as long as they do not hinder the purpose for which the composition is used. However, as long as the effects of the present invention are not impaired, the composition may optionally contain antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesion aids such as silane coupling agents, polymer matrix crosslinking agents, compatibilizers, curing agents, pigments, preservative stabilizers, defoaming agents, and the like.

[0251] [Content] There are no particular restrictions on the content of each component in the composition according to the embodiment of the present invention. There are no particular restrictions on the content of the nonlinear optically active polymer compound in the composition, but it is preferable to have a higher content of the component exhibiting nonlinear optical activity. For example, it is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, and even more preferably 10 to 100% by mass, based on the total mass of solids contained in the composition.

[0252] There are no particular restrictions on the content of organic solvents in the composition, but from the viewpoint of film uniformity, it is preferably 60 to 99% by mass of the total mass of the composition, more preferably 70 to 99% by mass, and even more preferably 80 to 98% by mass, from the viewpoint of ensuring the stability of the composition.

[0253] <Nonlinear Optical Element> An embodiment of the present invention comprises a film containing the above-mentioned polymer compound.

[0254] The nonlinear optical element is not particularly limited as long as it uses the above-mentioned composition or a nonlinear optically active polymer compound and operates based on a nonlinear optical effect, but examples include wavelength conversion elements, photorefractive elements, and electro-optic elements. Of these, nonlinear optical elements that operate based on an electro-optic effect are preferred, and more specifically, electro-optic elements such as optical switches, optical modulators, and phase shifters are preferred. In one embodiment, an optical modulator equipped with the above-mentioned nonlinear optical element can be used.

[0255] As an electro-optic element, it is preferable to use an element having a structure in which a film formed from the above-mentioned composition or a nonlinear optically active polymer compound is formed on a substrate and sandwiched between electrode pairs for input electrical signals.

[0256] There are no particular restrictions on the film thickness of the film formed from the above-mentioned composition or nonlinear optically active polymer compound, but to effectively utilize the nonlinear effect, it is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 0.8 μm or more. Furthermore, to avoid obstructing the guidance of light, it is preferably 50 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] The electro-optic element is preferably formed to include a waveguide structure, and it is particularly preferable to incorporate a film or nonlinear optically active polymer compound formed from the above-mentioned composition into the core layer of the waveguide.

[0261] A cladding layer (hereinafter also referred to as the "lower cladding layer" in this specification) may be formed between the core layer containing a film or nonlinear optically active polymer compound formed from the above-described composition and the substrate. This lower cladding layer can be any material that has a lower refractive index than the core layer and is not affected during the formation of the core layer. Preferred materials for forming the lower cladding layer include, for example, UV-curable or thermosetting resins such as acrylic, epoxy, oxetane, thiirane, and silicone resins; polyimide; and glass.

[0262] After forming a core layer with the above-described composition or nonlinear optically active polymer compound, a cladding layer (hereinafter also referred to as the "upper cladding layer" in this specification) may be formed on top of it in the same manner as the lower cladding layer. This forms a slab-type waveguide with the configuration of substrate / lower cladding layer / core layer / upper cladding layer.

[0263] 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.

[0264] 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.

[0265] When forming channel-type waveguides or ridge-type waveguides as described above, known device structures such as linear, Y-branch, directional coupler, and Mach-Zehender types can be configured as the core layer pattern, and these can be applied to known optical information communication devices such as optical switches, optical modulators, and phase shifters. One example of application to optical information communication devices is the application to an optical modulator equipped with a nonlinear optical element that operates based on the electro-optic effect described above.

[0266] 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.

[0267] <Synthesis of EO Polymers> EO polymer 1 and EO polymer 2 were synthesized using the following method.

[0268] <Synthesis of Compound 1>

[0269]

[0270] 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 1 (7.6 g, yield 77.6%).

[0271] <Synthesis of Compound 2>

[0272]

[0273] Under a nitrogen atmosphere, compound 1 (16.3 g, 56.1 mmol), diethyl-2-thienylmethylphosphonate (15.8 g, 67.3 mmol), and tetrahydrofuran (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 2 (17.4 g, yield 83.7%).

[0274] <Synthesis of Compound 3>

[0275]

[0276] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 2 (17.0 g, 45.8 mmol) and 2,4,6-trimethylaniline (9.3 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 3 (13.7 g, yield 70.3%).

[0277] <Synthesis of Compound 4>

[0278]

[0279] 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 DCM (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 4 (74.0 g, yield 50.4%).

[0280] <Synthesis of Compound 5>

[0281]

[0282] Under a nitrogen atmosphere, a solution of compound 4 (20.0 g, 72.2 mmol) in DMF (200 mL) was cooled to 0°C in a 500 mL flask, and then tert-butylmethylchlorosilane (TBDMSCl) (11.9 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 5 (22.9 g, yield 81.1%).

[0283] <Synthesis of Compound 6>

[0284]

[0285] Under a nitrogen atmosphere, in a 500 mL three-necked flask, a solution of compound 3 (11.9 g, 28.0 mmol) and compound 5 (13.1 g, 33.6 mmol) in toluene (186 mL) was prepared, to which sodium tert-butoxide (6.72 g, 69.9 mmol) and Pd were added. ２ (dba) ３ (512mg, 0.56mmol), tert-Bu ３ PHBF ４ After adding (649 mg, 2.24 mmol), the mixture was stirred at 100°C for 6.5 hours. After the reaction, water (400 mL) was added to the reaction solution and 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 (12.1 g, yield 62.9%).

[0286] <Synthesis of Compound 7>

[0287]

[0288] Under a nitrogen stream, a solution of compound 6 (12.0 g, 17.4 mmol) in tetrahydrofuran (120 mL) in a 500 mL three-necked flask was cooled to -78°C, and n-BuLi (1.6 M in Hexane, 12 mL) was added. After stirring at -78°C for 1 hour, DMF (5.4 mL) diluted with tetrahydrofuran (5.0 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 7 (9.09 g, yield 72.8%).

[0289] <Synthesis of Compound 8>

[0290]

[0291] Under a nitrogen stream, a solution of compound 7 (10.0 g, 14.0 mmol) in tetrahydrofuran (174 mL) was cooled to 0°C in a 500 mL three-necked flask, and hydrochloric acid (4.0 M in Water, 105 mL) was added. After addition, the temperature was raised to room temperature and stirred for 1.5 hours. The reaction solution was neutralized with sodium bicarbonate and extracted with dichloromethane. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 8 (7.26 g, yield 86.4%).

[0292] <Synthesis of Compound 9>

[0293]

[0294] Under a nitrogen atmosphere, a solution of compound 8 (5.0 g, 8.3 mmol) in tetrahydrofuran (83 mL) was cooled to 0°C in a 300 mL three-necked flask. Imidazole (904 mg, 13.3 mmol) and triphenylphosphine (2.9 g, 11.2 mmol) were added, followed by the slow addition of iodine (2.74 g, 10.8 mmol) in tetrahydrofuran (9 mL). After the addition, the mixture was heated to room temperature and stirred for 1 hour. After the reaction, saturated sodium thiosulfate aqueous solution (50 mL) was added to the reaction solution and extracted with ethyl acetate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 9 (5.03 g, yield 85.1%).

[0295] The results of the NMR measurement of compound 9 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ9.81 (s, 1H), 7.91 (d, 1H), 7.44-7.22 (m, 9H), 6.97 (s, 2H), 6.81 (d, 2H), 6.62 (d, 2H), 6.29 (d, 1H), 6.16 (dd, 2H), 4.99 (s, 2H), 3.65 (t, 2H), 3.30 (t, 2H), 2.90 (s, 3H), 2.29 (s, 3H), 1.89 (s, 6H)

[0296] <Nonlinear optically active compound 1>

[0297]

[0298] In a 100 mL three-necked flask, under a nitrogen stream, compound 9 (0.5 g, 1.27 mmol) and a solution of 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (340 mg, 1.08 mmol) in tetrahydrofuran (15 mL) were added, and the mixture was stirred at 25°C for 16 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 1 (390 mg, yield 52.2%).

[0299] The results of the NMR measurement of nonlinear optically active compound 1 are shown below. １ H-NMR (400MHz, CDCl ３) δ7.76 (d, 1H), 7.48-7.57 (m, 5H), 7.36-7.23 (m, 8H), 7.16 (d, 1H), 6.91-6.96 (m, 5H), 6.68 (d, 2H), 6.58 (d, 1 H), 6.37 (dd, 1H), 6.30 (d, 1H), 4.98 (s, 2H), 3.81 (t, 2H), 3.43 (t, 2H), 2.94 (s, 3H), 2.34 (s, 3H), 1.95 (s, 6H)

[0300] <Synthesis of base polymer 1'>

[0301]

[0302] Azobisisobutyronitrile (AIBN) (1.22 g, 0.37 mol) was added to a flask, purged with nitrogen, and dissolved in deoxygenated tetrahydrofuran (90 mL). Styrene (30.0 g, 0.26 mol) and 4-acetoxystyrene (18.0 g, 0.11 mol) were added. The reaction solution was heated to 65°C and stirred for 8 hours. After the reaction, the reaction solution was cooled to 0°C, and the reaction solution was added dropwise to hexane (1.8 L). After stirring at room temperature for 15 minutes, the resulting solid was filtered. The filtered solid was vacuum-dried at 50°C for 4 hours to obtain base polymer 1' (25.5 g).

[0303] The molecular weight of the obtained base polymer 1' was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: tetrahydrofuran, column temperature: 40°C). The weight-average molecular weight Mw was 19400, and the number-average molecular weight Mn was 12600.

[0304] <Synthesis of Base Polymer 1>

[0305]

[0306] Under a nitrogen atmosphere, concentrated hydrochloric acid (2.8 mL, 0.11 mol) was added to a solution of base polymer 1' (25.5 g, 0.21 mol) in ethanol (181 mL) in a 500 mL three-necked flask. After the addition, the temperature was raised to 90°C and stirred for 3.5 hours. After the reaction, the mixture was air-cooled to room temperature, and the reaction solution was poured into water (200 mL). The resulting solid was filtered and vacuum-dried at 50°C for 7 hours to obtain base polymer 1 (19.5 g).

[0307] The molecular weight of the obtained base polymer 1 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: tetrahydrofuran, column temperature: 40°C). The weight-average molecular weight Mw was 17,200 and the number-average molecular weight Mn was 10,600.

[0308] <Synthesis of EO Polymer 1'>

[0309]

[0310] Under a nitrogen atmosphere, base polymer 1 (2.00 g, 18.4 mmol) and compound 9 (654 mg, 0.92 mmol) were dissolved in dehydrated dimethylformamide (36.7 mL), potassium carbonate (7.61 g, 55.2 mmol) was added, and the mixture was stirred at room temperature for 50 minutes. The temperature was then raised to 50°C and the mixture was stirred for 3.5 hours. 1-iodohexane (1.4 mL) was added to the reaction solution, and the mixture was stirred at 50°C for a further 3.5 hours. After cooling to room temperature, the reaction solution was filtered, concentrated, and dispersed in methanol (100 mL). The methanol dispersion was sonicated, and the solid was filtered off. The filtered material was then washed with methanol (100 mL), isopropyl alcohol (100 mL), and hexane (100 mL). The resulting solid was vacuum-dried at 50°C for 4 hours to obtain EO polymer 1' (2.31 g, yield 79.9%).

[0311] The content of the group obtained by removing one hydrogen atom from the following compound 9 contained in EO polymer 1' was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content was found to be 17% by mass.

[0312] <Synthesis of EO Polymer 1>

[0313]

[0314] Under a nitrogen atmosphere, EO polymer 1' (1.31 g, 8.44 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (303 mg, 0.96 mmol) were dissolved in deoxygenated tetrahydrofuran (26.2 mL), then dehydrated ethanol (26.2 mL) was added, and the mixture was stirred at 50°C for 15 hours. After cooling to room temperature, the reaction solution was poured into a mixture of methanol and ultrapure water (mixing ratio 1:1,520 mL) and stirred at room temperature for 30 minutes. The resulting solid was filtered, and the filter was washed with methanol (260 mL). The filter was redissolved in dichloromethane (42 mL), filtered, and activated clay (1.4 g) was added to the filtrate and stirred at room temperature for 30 minutes. After removing the clay by filtration, activated clay (1.4 g) was added to the filtrate again, and the mixture was stirred at room temperature for 30 minutes. Then, the activated clay was removed by filtration, and the resulting filtrate was concentrated using an evaporator. It was redissolved in dichloromethane (15 mL) and added dropwise to methanol (700 mL). The resulting solid was filtered and rinsed with methanol (250 mL) to obtain EO polymer 1 (1.17 g, yield 83.0%).

[0315] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 1 contained in EO polymer 1 was determined from the ratio of mass extinction coefficients measured using a spectrophotometer, and the content was found to be 25% by mass (5 mol%).

[0316] <Synthesis of Compound 10> Compound 10 was synthesized in the same manner as compound 10b described in Journal of Polymer Science Part A: Polymer Chemistry, 2010, 49, 47-54.

[0317]

[0318] <Synthesis of Compound 11>

[0319]

[0320] In a 100 mL flask, a solution of compound 10 (1.00 g, 1.97 mmol) in tetrahydrofuran (10 mL) was stirred at 25°C, and a solution of tetrabutylammonium fluoride (TBAF) in tetrahydrofuran (1 M, 2.2 mL) was added dropwise. After addition, the mixture was stirred at 25°C for 3 hours. After the reaction was complete, water (50 mL) was added, and the mixture was extracted with DCM (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compound 11 (722 mg, yield 88.8%).

[0321] The results of the NMR measurement of compound 11 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ9.79 (s, 1H), 7.60 (d, 1H), 7.33-7.48 (m, 7H), 7.14 (d, 1H), 6.99 (d, 1H), 6. 39 (dd, 1H), 6.30 (d, 1H), 3.78 (dd, 2H), 3.49 (t, 2H), 3.01 (t, 3H), 1.60 (t, 1H)

[0322] <Synthesis of Nonlinear Optically Active Compound 2>

[0323]

[0324] In a 100 mL three-necked flask, under a nitrogen stream, compound 11 (0.5 g, 1.27 mmol) and a solution of 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (521 mg, 1.65 mmol) in tetrahydrofuran (5 mL) were added, to which ethanol (10 mL) was added and the mixture was stirred at 25 °C for 16 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 2 (581 mg, yield 66.2%).

[0325] The results of the NMR measurement of nonlinear optically active compound 2 are shown below. １ H-NMR (400MHz, CDCl３ ) δ7.78 (d, 1H), 7.46-7.58 (m, 8H), 7.35-7.44 (m, 4H), 7.15 (d, 1H), 6.92 (d, 1H), 6.55 (d, 1H), 6.39 (d, 1H), 6.28 (s, 1H), 5.20 (s, 2H), 3.78 (t, 2H), 3.53 (t, 2H), 3.05 (s, 3H)

[0326] <Synthesis of Base Polymer 2>

[0327]

[0328] Methyl methacrylate (MMA) (100.0 g, 1.00 mol) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (62.7 g, 0.25 mol) were dissolved in deoxygenated toluene (375 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (620 mg, 25 mmol) were added. After purging with nitrogen, the reaction solution was heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to hexane (2.5 L), and the resulting solid was filtered. The filtered solid was dissolved in tetrahydrofuran (1.25 L) and filtered. The filtrate was concentrated to 700 mL using an evaporator, and then added dropwise to methanol (6.7 L), and stirred at room temperature for 30 minutes. The solid was then filtered off, and the filtered material was rinsed with methanol (2.2 L). After that, base polymer 2 was obtained by vacuum drying at 60°C for 8 hours (110 g).

[0329] The molecular weight of the obtained base polymer 2 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: tetrahydrofuran, column temperature: 40°C). The weight-average molecular weight Mw was 70,600, and the number-average molecular weight Mn was 38,900.

[0330] <Synthesis of EO Polymer 2>

[0331]

[0332] Under a nitrogen atmosphere, base polymer 2 (30.0 g, 0.22 mol) and nonlinear optically active compound 2 (7.58 g, 11 mmol) were dissolved in deoxygenated 1,4-dioxane (450 mL) and stirred at room temperature for 5 minutes. Then, dibutyltin dilaurate (DBTDL) (6.6 mL) was added and the mixture was stirred in an oil bath at 100°C for 2 hours. Subsequently, dehydrated methanol (35.5 mL) was added and the mixture was stirred in an oil bath at 100°C for 1 hour. 24 mL of the reaction solution was withdrawn and added dropwise to hexane (240 mL), and the resulting solid was filtered off. The filtered solid was rinsed with hexane (240 mL) to obtain EO polymer 2 (1.33 g).

[0333] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 2 contained in EO polymer 2 was determined from the ratio of mass extinction coefficients measured using a spectrophotometer, and the content was found to be 23 mass% (5 mol%).

[0334] <Synthesis of Monomer 1>

[0335]

[0336] Under a nitrogen atmosphere, triphenylphosphine (1.0 g, 3.81 mmol) was added to a solution of 4-hydroxyphenyl methacrylate (543 mg, 3.05 mmol) and compound 11 (1.0 g, 2.54 mmol) in deoxygenated tetrahydrofuran (10.2 mL). After cooling to 0°C, a toluene solution of diethyl azodicarboxylate (DEAD) (2.4 M, 1.6 mL, 3.81 mmol) was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred for 18 hours. After the reaction was complete, the solvent was removed using an evaporator, and monomer 1 (551 mg, yield 38.6%) was obtained by purification using silica gel column chromatography.

[0337] The results of the NMR measurement of monomer 1 are shown below. １ H-NMR (400MHz, CDCl ３) δ9.80 (s, 1H), 7.61 (d, 1H), 7.41-7.48 (m, 3H), 7.37-7.40 (m, 3H), 7.33 (d, 1H), 7.14 (d, 1H), 6.97-7.04 (m, 3H), 6.81-6.86 (m , 2H), 6.38 (dd, 1H), 6.32 (s, 1H), 6.27 (d, 1H), 5.73 (dd, 1H), 5.16 (s, 2H), 4.04 (t, 2H), 3.74 (t, 2H), 3.07 (s, 3H), 2.05 (s, 3H)

[0338] <Synthesis of EO Polymer 3'>

[0339]

[0340] Methyl methacrylate (MMA) (1.0 g, 9.98 mmol) and monomer 1 (0.5 g, 0.90 mmol) were dissolved in deoxygenated N,N-dimethylformamide (6.3 mL) and stirred for 5 minutes. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (10.8 mg, 0.043 mmol) was added, and the mixture was stirred for another 5 minutes at room temperature. The reaction solution was then heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to methanol (126 mL). The resulting solid was filtered and dried under reduced pressure. The obtained solid was dissolved in dichloromethane (18 mL), and methanol (126 mL) was slowly added dropwise while stirring. After removing the supernatant, the residue was rinsed with methanol (18 mL). The residue was redissolved in dichloromethane (18 mL), filtered, and then rinsed with dichloromethane (18 mL). The filtrate was concentrated using an evaporator until it reached 12.2 g. The concentrate was added dropwise to methanol (120 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, the filtered material was rinsed with methanol (120 mL), and then vacuum-dried at 50°C for 5 hours to obtain EO polymer 3' (465 mg).

[0341] <Synthesis of EO Polymer 3>

[0342]

[0343] Under a nitrogen atmosphere, EO polymer 3' (440 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (251 mg, 0.80 mmol) were dissolved in deoxygenated tetrahydrofuran (8.8 mL), then anhydrous ethanol (8.8 mL) was added, and the mixture was stirred at 50°C for 15 hours. After cooling to room temperature, the reaction solution was concentrated in an evaporator and redissolved in dichloromethane (7.8 mL). The solution was added to hexane (156 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, and the filter was rinsed with hexane (78 mL). The filter was redissolved in dichloromethane (18 mL), and methanol (72 mL) was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:4) (18 mL). The residue was redissolved in dichloromethane (18 mL), filtered, and the filtrate was concentrated in an evaporator until it reached 12.5 g. The concentrated solution was added dropwise to methanol (141 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, the filtered material was rinsed with methanol (70 mL), and then vacuum-dried at 50°C for 5 hours to obtain EO polymer 3 (416 mg).

[0344] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 2 contained in EO polymer 3 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content was found to be 43 mass% (10 mol%).

[0345] <Synthesis of Compound 13>

[0346]

[0347] Under a nitrogen atmosphere, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (12.5 g, 75.2 mmol) and 4-aminophenol (8.21 g, 75.2 mmol) were dissolved in acetic acid (18.8 mL), and the mixture was heated under reflux for 10 minutes. Acetic acid (56.2 mL) was added, and the mixture was stirred under reflux for another 20 minutes. After the reaction solution was air-cooled to room temperature, water (75 mL) was added and the mixture was stirred for 20 minutes. The resulting solid was filtered, and the filtered material was rinsed three times with water (75 mL). Compound 13 (6.83 g, 35.3%) was obtained by dissolving the rinsed solid in methanol and recrystallizing it.

[0348] <Synthesis of Compound 14>

[0349]

[0350] Under a nitrogen atmosphere, triphenylphosphine (7.65 g, 29.1 mmol) was added to a solution of compound 11 (7.65 g, 19.4 mmol) and compound 13 (6.0 g, 23.3 mmol) in deoxygenated tetrahydrofuran (77.7 mL). After cooling to 0°C, a toluene solution of diethyl azodicarboxylate (DEAD) (2.4 M, 12.1 mL, 29.1 mmol) was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred for 6.5 hours. After the reaction was complete, the solvent was removed using an evaporator, and compound 14 (5.35 g, yield 43.0%) was obtained by purification using silica gel column chromatography.

[0351] <Synthesis of Monomer 2>

[0352]

[0353] Under a nitrogen atmosphere, a solution of compound 14 (5.33 g, 8.33 mmol) in toluene (107 mL) was heated to reflux temperature and stirred for 1.5 hours. The solvent was then removed using an evaporator. The residue was redissolved in toluene (107 mL) under a nitrogen atmosphere and stirred at reflux temperature for 1.5 hours. After the reaction was complete, the solvent was removed using an evaporator, and monomer 2 (4.15 g, yield 88.2%) was obtained by purification using silica gel column chromatography.

[0354] The results of the NMR measurement of monomer 2 are shown below. １H-NMR (400MHz, CDCl ３ ) δ9.80 (s, 1H), 7.61 (d, 1H), 7.31-7.49 (m, 7H), 7.23 (dt, 2H), 7.15 (d, 1H), 7.00 (d, 1H), 6.91 (dt , 2H), 6.83 (s, 2H), 6.36 (dd, 1H), 6.27 (d, 1H), 5.16 (s, 2H), 4.07 (t, 2H), 3.75 (t, 2H), 3.07 (s, 3H)

[0355] <Synthesis of EO Polymer 4'>

[0356]

[0357] Styrene (1.12 g, 10.8 mmol), N-ethylmaleimide (1.10 g, 8.75 mmol), and monomer 2 (1.13 g, 2.0 mmol) were added to a flask, purged with nitrogen, dissolved in deoxygenated DMF (56.3 mL), and 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (21.4 mg, 0.09 mmol) was added. The reaction solution was heated to 60°C and stirred for 6 hours. Then the temperature was raised to 70°C and stirred for a further 2 hours. After the reaction solution was air-cooled to room temperature, it was added dropwise to methanol (563 mL), and the resulting solid was filtered. The filtered solid was dissolved in tetrahydrofuran (53 mL), filtered, and then rinsed with tetrahydrofuran (53 mL). The filtrate was concentrated in an evaporator until it reached 35.5 g. The concentrate was added dropwise to methanol (413 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered and vacuum-dried at 50°C for 5 hours to obtain EO polymer 4' (1.5 g).

[0358] <Synthesis of EO Polymer 4>

[0359]

[0360] Under a nitrogen atmosphere, EO polymer 4' (778 mg) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malononitrile (440 mg, 1.40 mmol) were dissolved in deoxygenated tetrahydrofuran (15.6 mL), then anhydrous ethanol (15.6 mL) was added, and the mixture was stirred at 50°C for 15.5 hours. After cooling to room temperature, the reaction solution was concentrated in an evaporator and redissolved in dichloromethane (13.8 mL). The solution was added to hexane (138 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, and the filter was rinsed with hexane (70 mL). The filter was redissolved in dichloromethane (24 mL), and methanol (72 mL) was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio 1:3) (24 mL). The residue was redissolved in dichloromethane (24 mL), filtered, and the filtrate was concentrated in an evaporator until it reached 18.6 g. The concentrated solution was added dropwise to methanol (165 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, the filtered material was rinsed with methanol (140 mL), and then vacuum-dried at 50°C for 6 hours to obtain EO polymer 4 (736 mg).

[0361] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 2 contained in EO polymer 4 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content was found to be 31% by mass (9 mol%).

[0362] <Synthesis of Compound 15>

[0363]

[0364] Under a nitrogen atmosphere, 2,4,6-trimethylaniline (43.3, 0.32 mmol) was dissolved in ethanol (640 mL) and iodoethane (50.0 g, 0.32 mmol) and potassium carbonate (88.6 g, 0.64 mmol) were added sequentially, and the mixture was stirred at reflux temperature for 6 hours. The reaction solution was air-cooled, and the solution was removed by evaporation. Water (200 mL) was added to the residue, and it was extracted with ethyl acetate (200 mL). The organic layer was washed with water (100 mL) and saturated sodium chloride aqueous solution (100 mL), dried over sodium sulfate, and filtered. The filtrate was concentrated using an evaporator and purified by silica gel column chromatography to obtain compound 15 (23.0 g, yield 41.1%).

[0365] <Synthesis of Compound 16> Compound 16, described below, was synthesized in the same manner as compound 23 described in International Publication No. 2025 / 205646.

[0366]

[0367] <Synthesis of Compound 17>

[0368]

[0369] Compound 15 (8.4 g, 51.7 mmol) was added to a solution of compound 16 (26.2 g, 43.1 mmol) in toluene (262 mL), and the mixture was bubbled with argon at room temperature for 20 minutes. Then, sodium tert-butoxide (5.79 g, 60.3 mmol) and Pd, which had been stirred at room temperature for 20 minutes beforehand, were added. ２ (dba) ３ A solution of (394 mg, 0.43 mmol) and XPhos (821 mg, 1.72 mmol) in toluene (20 mL) was added. After addition, the reaction solution was stirred at 90°C for 3.5 hours. After the reaction was complete, water (200 mL) was added to the reaction solution and extracted with dichloromethane. The organic layer was dried using an evaporator and purified by silica gel column chromatography to obtain compound 17 (20.5 g, yield 71.8%).

[0370] <Synthesis of Compound 18>

[0371]

[0372] Under a nitrogen atmosphere, a solution of compound 17 (20.4 g, 30.9 mmol) in deoxygenated tetrahydrofuran (278 mL) was sequentially mixed with methanol (92.7 mL) and p-toluenesulfonic acid monohydrate (294 mg, 1.55 mmol), and the mixture was stirred at room temperature for 4 hours. After the reaction was complete, the mixture was neutralized with saturated sodium bicarbonate aqueous solution and extracted with dichloromethane (200 mL). The organic layer was washed with water (200 mL) and saturated sodium chloride aqueous solution (200 mL), dried over sodium sulfate, and filtered. The filtrate was concentrated using an evaporator and purified by silica gel column chromatography to obtain compound 18 (14.0 g, yield 78.6%).

[0373] <Synthesis of Compound 19>

[0374]

[0375] Under a nitrogen atmosphere, a solution of compound 18 (13.5 g, 23.3 mmol) in toluene (466 mL) was cooled to -74°C, and a hexane solution of diisobutylaluminum hydride (DIBAL-H) ​​(1 M, 56 mL, 55.9 mmol) was slowly added. After addition, the mixture was stirred at -74°C to -62°C for 2 hours, and then stirred at -40°C for 1.5 hours. The mixture was then cooled again to -74°C, and a hexane solution of diisobutylaluminum hydride (DIBAL-H) ​​(1 M, 4.7 mL, 4.66 mmol) was slowly added. After addition, the mixture was stirred at -40°C for 2 hours. After the reaction was complete, water (1 L) was added to the reaction solution, and it was extracted with ethyl acetate. The organic layer was dried using an evaporator, and compound 19 (7.26 g, yield 53.7%) was obtained by purification by silica gel column chromatography.

[0376] <Synthesis of Nonlinear Optically Active Compound 3>

[0377]

[0378] Under a nitrogen atmosphere, a solution of compound 19 (150 mg, 0.26 mmol) and 2-[3-cyano-4,5,5-trimethyl-furan-2(5H)-ylidene]malononitrile (515 mg, 2.6 mmol) in tetrahydrofuran (10 mL) was mixed with ethanol (10 mL) and stirred at 60°C for 16 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain nonlinear optically active compound 3 (80 mg, yield 40.6%).

[0379] The results of the NMR measurement of nonlinear optically active compound 3 are shown below. １ H-NMR (400MHz, CDCl ３ ) δ8.03 (t, 1H), 7.24-7.52 (m, 10H), 6.93 (s, 2H), 6.79 (d, 1H), 6.29 (d, 1H), 4.98 (s, 2H), 3.87 (d, 4H), 3 .56 (q, 2H), 2.48 (d, 4H), 2.34 (s, 3H), 2.10 (s, 1H), 1.95 (s, 5H), 1.68 (s, 6H), 1.16 (t, 3H), 1.04 (s, 6H)

[0380] <Synthesis of Monomer 3>

[0381]

[0382] Under a nitrogen atmosphere, triphenylphosphine (1.36 g, 5.18 mmol) was added to a solution of 4-isopropenylphenol (694 mg, 5.17 mmol) and compound 19 (2.0 g, 3.45 mmol) in deoxygenated tetrahydrofuran (34.5 mL). After cooling to 0°C, a toluene solution of diethyl azodicarboxylate (DEAD) (2.4 M, 2.2 mL, 5.28 mmol) was slowly added dropwise. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred for 5 hours. After the reaction was complete, the solvent was removed using an evaporator, and monomer 3 (1.07 mg, yield 44.4%) was obtained by purification using silica gel column chromatography.

[0383] The results of the NMR measurement of monomer 3 are shown below. １ H-NMR (400MHz, CDCl ３) δ10.02 (d, 1H), 7.28-7.37 (m, 9H), 7.06 (d, 1H), 7.96 (s, 2H), 7.92 (dt, 2H), 6.27 (d, 1H), 5.98 (s, 1H), 5.91 (d, 1H), 5.25 (s, 1H), 5.02 (s, 2H), 4 98 (t, 1H), 4.24 (dd, 2H), 3.97 (dd, 2H), 3.52 (q, 2H), 2.77 (s, 2H), 2.35 (s, 2H), 2.29 (s, 3H), 2.06 (s, 3H), 1.93 (s, 6H), 1.08 (t, 3H), 1.02 (s, 6H)

[0384] <Synthesis of EO Polymer 5'>

[0385]

[0386] α-methylstyrene (806 mg, 6.82 mmol), ethyl maleimide (1.03 g, 8.26 mmol), and monomer 3 (1.0 g, 1.44 mmol) were dissolved in deoxygenated N,N-dimethylformamide (6.0 mL) and stirred for 5 minutes. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (16.4 mg, 0.066 mmol) was added and the mixture was stirred for another 5 minutes at room temperature. The reaction solution was then heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C and stirred for another 2 hours. After the reaction, the reaction solution was cooled to 0°C and added dropwise to methanol (90 mL). The resulting solid was filtered and dried under reduced pressure. The obtained solid was dissolved in dichloromethane (10.6 mL) and methanol (63.6 mL) was slowly added dropwise while stirring. After removing the supernatant, the residue was rinsed with a mixed solution of dichloromethane and methanol (mixing volume ratio, 1:6) (10.6 mL). The residue was redissolved in dichloromethane (10.6 mL), filtered, and then rinsed with dichloromethane (10.6 mL). The filtrate was concentrated using an evaporator until it reached 10.8 g. The concentrate was added dropwise to methanol (80 mL) and stirred at room temperature for 20 minutes. The resulting solid was filtered, the filtered material was rinsed with methanol (40 mL), and then vacuum-dried at 50°C for 5 hours to obtain EO polymer 5' (336 mg).

[0387] <Synthesis of EO Polymer 5>

[0388]

[0389] Under a nitrogen atmosphere, 150 mg of EO polymer 5' and 137 mg, 0.69 mmol of 2-[3-cyano-4,5,5-trimethyl-furan-2(5H)-ylidene]malononitrile were dissolved in 7.5 mL of tetrahydrofuran, to which 7.5 mL of ethanol was added and the mixture was stirred at 60°C for 16 hours. After cooling to room temperature, the reaction solution was concentrated using an evaporator and redissolved in 2.0 mL of dichloromethane. The solution was added to 100 mL of hexane and stirred at room temperature for 20 minutes. The resulting solid was filtered, and the filter was rinsed with 50 mL of hexane. The filter was redissolved in 2.0 mL of dichloromethane, and 10 mL of methanol was slowly added dropwise while stirring. The supernatant was removed, and the residue was rinsed with 10 mL of a mixed solution of dichloromethane and methanol (mixing volume ratio 1:5). The residue was redissolved in dichloromethane (2.0 mL), added dropwise to methanol (100 mL), and stirred at room temperature for 20 minutes. The resulting solid was filtered, the filtered material was rinsed with methanol (50 mL), and then vacuum-dried at 50°C for 6 hours to obtain EO polymer 5 (82 mg).

[0390] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 3 contained in EO polymer 5 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content was found to be 6% by mass (2 mol%).

[0391] <Synthesis of base polymer 3>

[0392]

[0393] Phenylmaleimide (6.2 g, 35.8 mmol) and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (3.0 g, 11.9 mmol) were dissolved in deoxygenated N,N-dimethylformamide (14.5 mL), and then 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65) (47.4 mg, 0.19 mmol) was added. After purging with nitrogen, the reaction solution was heated to 60°C and stirred for 6 hours, then the temperature was raised to 70°C and stirred for a further 2 hours. The reaction solution was air-cooled, diluted with tetrahydrofuran (184 mL), and then added dropwise to methanol (1.1 L), and stirred at room temperature for 20 minutes. The resulting solid was filtered, dissolved in tetrahydrofuran (184 mL), and filtered. The filtrate was concentrated in an evaporator until it reached 123.4 g. The concentrated solution was added dropwise to methanol (1.42 L) and stirred at room temperature for 20 minutes. The resulting solid was filtered off, and the filtered material was rinsed with methanol (0.7 L). Base polymer 3 was obtained by vacuum drying at 50°C for 5 hours (5.89 g).

[0394] The molecular weight of the obtained base polymer 3 was determined by GPC using a Shimadzu Corporation GPC system (liquid delivery system: LC-20AD, detector: RID) (columns: TSKgel SuperMultiporeHZ-M (4.6 mm ID × 150 mm L, 4 μm, S) × 2, TSKguardcolumn SuperMP(HZ)-M, developing solvent: LiBr (0.5 wt%) in NMP, column temperature: 40°C). The weight-average molecular weight Mw was 28,000 and the number-average molecular weight Mn was 9,000.

[0395] <Synthesis of EO Polymer 6>

[0396]

[0397] Under a nitrogen atmosphere, base polymer 3 (300 mg) and nonlinear optically active compound 2 (68 mg, 0.1 mmol) were dissolved in deoxygenated 1,4-dioxane (8.3 mL), stirred at room temperature for 5 minutes, then dibutyltin dilaurate (DBTDL) (32 mg) was added and the mixture was stirred in an oil bath at 110°C for 2 hours. Subsequently, dehydrated methanol (42 μL) was added and the mixture was stirred in an oil bath at 100°C for 1 hour. After the reaction solution was air-cooled, it was added dropwise to methanol (150 mL), and the resulting solid was filtered off. The filtered solid was rinsed with methanol (50 mL) to obtain EO polymer 6 (280 mg).

[0398] The content of the group obtained by removing one hydrogen atom from the nonlinear optically active compound 2 contained in EO polymer 6 was determined from the ratio of mass extinction coefficients in absorbance measurements using a spectrophotometer, and the content was found to be 21% by mass (6 mol%).

[0399] <Evaluation Equipment> The following equipment was used for the evaluation below. TG-DTA: Differential thermal energy simultaneous measurement device STA-200 manufactured by Hitachi High-Tech Corporation Vacuum constant temperature drying oven: DP-23 manufactured by Yamato Scientific Co., Ltd.

[0400] (Example 1) <Heat drying process for solvent and moisture removal> The EO polymer 1 synthesized as described above was dried in a vacuum constant-temperature dryer at 110°C for 3 hours.

[0401] <Quantitative Evaluation of Residual Solvent and Moisture Content by TG-DTA and Evaluation of Decomposition Temperature> EO Polymer 1, which underwent the above heat drying process, was weighed into an Al pan (product name "Al open-type sample container, Φ5.2 H2.5 mm", manufactured by Hitachi High-Tech Science Corporation), and the temperature was raised to 400°C at 10°C / min. TG-DTA was measured to confirm the weight loss. As a result, the mass loss up to 180°C was 0.1%. Subsequently, the temperature at which a 5% mass loss occurred was 369°C, and above this temperature, a significant mass loss due to the decomposition of the dye or polymer was observed. Normally, a mass loss of 0.5% or less is considered to be due to moisture adsorption during the evaluation procedure, etc., and not a mass loss due to residual solvent or moisture in the compound. Therefore, this measurement suggests that EO Polymer 1 does not contain residual solvent or moisture and is sufficiently dried. The results are shown in Table 3.

[0402] <Evaluation of Filterability> The EO polymer 1 that underwent the above heat drying process was weighed to a solid content concentration of 13% by mass and dissolved in cyclohexanone. The resulting cyclohexanone solution was filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm. As a result, the time required to filter 0.2 ml of the cyclohexanone solution was less than 5 seconds. This measurement suggests that viscosity increase and gelation due to the heat drying process were suppressed in EO polymer 1. In the evaluation of filterability, the time required to filter 0.2 ml of the cyclohexanone solution was evaluated as "A" if it was less than 5 seconds, "B" if it took 5 seconds or more, and "C" if no liquid passed through. The results are shown in Table 3.

[0403] (Comparative Example 1) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 2. The results are shown in Table 3. Although drying was sufficient, the filtration performance was worse compared to when EO polymer 1 was used. The temperature at which a 5% mass loss occurred was 278°C.

[0404] (Comparative Example 2) The same evaluation as in Comparative Example 1 was performed, except that the drying temperature and time were changed to 85°C and 3 hours. The results are shown in Table 3. There was no residual solvent, and drying was considered to be sufficient, but the filterability was worse compared to when EO polymer 1 was used.

[0405] (Comparative Example 3) The same evaluation as in Comparative Example 1 was performed, except that the drying temperature and time were changed to 80°C and 6 hours. The results are shown in Table 3. There was some residual solvent, but drying was sufficient and filterability was ensured.

[0406] (Comparative Example 4) The same evaluation as in Comparative Example 1 was performed, except that the drying temperature and time were changed to 50°C and 8 hours. The results are shown in Table 3. Residual solvent and other substances were observed, indicating insufficient drying, but filterability was ensured.

[0407]

[0408] (Example 2) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 3. The results are shown in Table 4. The mass loss up to 180°C was 0.2%, and the temperature at which a 5% mass loss occurred was 280°C. Drying was sufficient, and the filterability was also good. The results are shown in Table 4.

[0409] (Example 3) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 4. The results are shown in Table 4. The mass loss up to 180°C was 0.4%, and the temperature at which a 5% mass loss occurred was 339°C. Drying was sufficient, and the filterability was also good. The results are shown in Table 4.

[0410] (Comparative Example 5) The same evaluation as in Example 1 was performed, except that EO polymer 1 was changed to EO polymer 6. The results are shown in Table 4. The mass loss up to 180°C was 1.1%, and the temperature at which a 5% mass loss occurred was 279°C. Drying was also insufficient, and the filterability was worse compared to the example. The results are shown in Table 4.

[0411]

[0412] As described above, when using the comparative polymer compounds (EO polymer 2, EO polymer 6), there was an upper limit to the drying temperature and a long drying time was required to satisfy the conditions for removing residual solvent and ensuring filtration. In contrast, the polymer compounds of the examples (EO polymer 1, EO polymer 3, EO polymer 4) were found to have a higher upper limit to the drying temperature and good filtration. Furthermore, the thermal decomposition temperature (temperature of 5% mass loss) of the polymer compounds of the examples was higher than that of the polymer compounds of the comparative examples, indicating that the thermal durability of the polymer compounds according to the embodiment of the present invention was greatly improved.

[0413] Although various embodiments have been described above, it goes without saying that the present invention is not limited to these examples. It is clear to those skilled in the art that various modifications or alterations can be conceived within the scope of the claims, and these will naturally also fall within the technical scope of the present invention. Furthermore, the components in the above embodiments may be combined in any way without departing from the spirit of the invention.

[0414] This application is based on Japanese Patent Application No. 2025-009459 filed on January 22, 2025, and Japanese Patent Application No. 2025-048741 filed on March 24, 2025, the contents of which are incorporated by reference in this application.

[0415] The polymer compounds according to the embodiments of the present invention exhibit suppressed viscosity increase and gelation during heating, and have excellent thermal stability, making them suitable for use in nonlinear optical elements or optical modulators equipped therewith.

Claims

1. A polymer compound containing a repeating unit represented by the following formula (1). [In formula (1), A １１ represents a trivalent group obtained by removing two hydrogen atoms from a group selected from the following hydrocarbon group A which may have a substituent, a trivalent aromatic group which may have a substituent, a trivalent heterocyclic group which may have a substituent, or a trivalent amino group which may have a substituent. A １２ and A １３ each independently represent a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A which may have a substituent, a divalent aromatic group which may have a substituent, or a divalent heterocyclic group which may have a substituent, a carbonyl group, or an oxygen atom. R １１ each independently represents a group selected from the following hydrocarbon group A which may have a substituent, or an aromatic group which may have a substituent. When n １２ is 2 or more, the R １１ may be bonded to another R １１ to form a ring. L １１ each independently represents a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A which may have a substituent, an oxygen atom, a carbonyl group, a divalent aromatic group which may have a substituent, or a divalent heterocyclic group which may have a substituent. X １１ each independently represents a group obtained by removing one hydrogen atom from a compound represented by the following formula (2). n １１ is an integer of 1 to 5. n １２ is an integer of 0 to 4. n １３ is an integer of 0 to 5. n １４ and n １５ each independently is an integer of 0 to 5. However, the sum of n １１ and n １２ is 5 or less. ] [In formula (2), Ar ２１ each independently represents a divalent aromatic group which may have a substituent. R ２１ and R ２３ Each of these is independently a divalent group obtained by removing one hydrogen atom from a group selected from the following hydrocarbon group A, which may have substituents, or a divalent aromatic group which may have substituents, and R ２２ and R ２４ Each independently represents a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, an aromatic group which may have substituents, an amino group which may have substituents, a hydroxyl group which may have substituents, or a halogen atom, Y ２１ Each is independently a divalent π-conjugated linkage group which may have substituents, and Z ２１ This is a group represented by the following formula (3), and m ２１ Each of these is an integer between 0 and 5, and m ２２ m is an integer between 1 and 5. ２３ n is an integer between 0 and 5. ２１ [This is an integer between 1 and 15.] [In formula (3), *J ３１ Y ２１ This represents the bonding position with R ３１ and R ３２ Each independently represents a group selected from the following hydrocarbon group A, which may have substituents, or an aromatic group which may have substituents, R ３１ and R ３２ They may be bonded together to form a ring, or R ３１ and R ３２ R ３１ and R ３２ These may also form a carbonyl group together with the carbon atom to which they are bonded, R ３３ ~R ３５ Each independently represents a cyano group, a C2-C30 alkyloxycarbonyl group which may have substituents, or a C1-C30 alkylsulfonyl group which may have substituents, X ３１ is an oxygen atom, a sulfur atom, or N-Q ３１ This represents Q ３１ represents a hydrogen atom, a group selected from the following hydrocarbon group A which may have substituents, or an aralkyl group which may have substituents. ] <Hydrogen group A> A branched, linear or cyclic alkyl group having 1 to 30 carbon atoms, a branched, linear or cyclic alkenyl group having 2 to 30 carbon atoms, or a branched, linear or cyclic alkynyl group having 2 to 30 carbon atoms, in which part of the carbon chain may be substituted with an oxygen atom, a sulfur atom, an aromatic hydrocarbon group and / or a silicon atom.

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

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

4. A in the formula (1) １１ The polymer compound according to claim 1, wherein each A is independently represented by the following formula (8) or the following formula (9). [In formula (8), R ８１ to R ８３ each independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, or a halogen atom, and *J ８１ represents the bonding position with L １１ .] [In formula (9), R ９１ and R ９２ each independently represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, and *J ９１ represents the bonding position with L １１ .] 5. The polymer compound according to claim 1, further comprising a repeating unit represented by the following formula (11). [In formula (11), R １１１ ~R １１６ are each independently a group selected from the hydrocarbon group A which may have a substituent and may be a hydrogen atom, and L １１１ and L １１２ are each independently a divalent group obtained by removing one hydrogen atom from a group selected from the hydrocarbon group A which may have a substituent, an oxygen atom, a carbonyl group, a divalent aromatic group which may have a substituent, or a divalent heterocyclic group which may have a substituent, Y １１１ and Y １１２ are each independently a hydrogen atom, a group selected from the hydrocarbon group A which may have a substituent, an aromatic group which may have a substituent, or a heterocyclic group which may have a substituent, a hydroxy group, an amino group which may have a substituent, or a silyl group which may have a substituent, R １１３ ~R １１６ , L １１１ and L １１２ may be bonded to each other to form a ring, and n １１１ and n １１２ are each independently an integer of 0 to 5. ] 6. A composition comprising a polymer compound according to any one of claims 1 to 5 and an organic solvent.

7. A nonlinear optical element comprising a film containing a polymer compound according to any one of claims 1 to 5.

8. The nonlinear optical element according to claim 7, which operates based on the electro-optic effect.

9. An optical modulator comprising the nonlinear optical element described in claim 7.

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