Compounds, nonlinear-optically active high-molecular compounds, compositions, nonlinear-optical elements, and optical modulators

Abstract

Disclosed is a compound in which an EO coefficient is increased in accordance with a concentration thereof even in a state in which the compound is dispersed or bonded to a medium such as a high-molecular material at a high concentration. Also disclosed are a composition containing the compound, a nonlinear optical element formed using the composition, and an optical modulator provided with the nonlinear optical element and operating based on an electro-optic effect. The present application relates to a compound represented by the following formula (1). (The definitions of the groups in formula (1) are described in the specification.)

Description

Technical Field

[0001] This invention relates to compounds, nonlinear optically active polymers, compositions, nonlinear optical elements, and optical modulators. Background Technology

[0002] In recent years, the development of various optoelectronic components utilizing nonlinear optical materials has been advancing 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. Materials that produce the first-order electro-optic effect (Pockels effect), a second-order nonlinear optical effect, are being considered for applications such as optical switches and optical modulation.

[0003] Previously, lithium niobate and potassium dihydrogen phosphate, as inorganic nonlinear optical materials, have been put into practical use and are widely used. However, in recent years, compared with these inorganic materials, organic nonlinear optical materials have attracted attention due to their advantages such as high nonlinear optical performance, low material cost, and high mass production capability, and are currently undergoing active research and development for practical application.

[0004] Organic nonlinear optical materials are typically obtained by dispersing or bonding nonlinearly optically active compounds (dyes) to polymers such as polymethyl methacrylate (PMMA). The nonlinear optical properties are represented by the electro-optic coefficient (hereinafter also referred to as the "EO coefficient"), denoted as r33. To exhibit the electro-optic effect, nonlinear optical materials require the orientation of the nonlinearly optically active compound. The orientation of the nonlinearly optically active compound can be achieved by applying an electric field at a temperature near the glass transition temperature (Tg) of the electro-optic polymer, then lowering the temperature to room temperature while the electric field is applied, and finally removing the electric field. As nonlinear optical compounds, so-called push-pull type π-conjugated compounds are known, having electron-donating and electron-accepting groups located at opposite ends of the molecular structure, and π-conjugated chains connecting them. It is desirable for nonlinear optical materials to possess a high EO coefficient, high heat resistance, and low absorption loss at wavelengths used in optical communication (Patent Documents 1-4).

[0005] One method to improve the EO coefficient is to increase the concentration of a compound with nonlinear optical activity relative to the polymer material. It is known that the EO coefficient is related to the concentration of the compound with nonlinear optical activity relative to the polymer material. (Patent Documents 5-6 and Non-Patent Document 1)

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2019 / 151318

[0009] Patent Document 2: Japanese Patent Application Publication No. 2010-066325

[0010] Patent Document 3: International Publication No. 2011 / 024774

[0011] Patent Document 4: Japanese Patent Application Publication No. 2015-178544

[0012] Patent Document 5: International Publication No. 2013 / 172342

[0013] Patent Document 6: Japanese Patent Application Publication No. 2014-130196

[0014] Non-patent literature

[0015] Non-patent literature 1: Journal of Polymer Science Part A: Polymer Chemistry, 2010, Vol.49, Issue 1, pp.47-54. Summary of the Invention

[0016] The problem that the invention aims to solve

[0017] However, compounds with nonlinear optical activity have large dipole moments, resulting in strong intermolecular interactions and poor dispersibility in media. Therefore, it is known that when increasing the concentration of the nonlinear optically active compound relative to polymeric materials such as PMMA (an example of a medium), the EO coefficient no longer increases beyond a certain concentration level. Furthermore, the same phenomenon has been observed when the nonlinear optically active compound is bonded to a polymeric compound.

[0018] In view of the above-mentioned technical problems, the present invention aims to provide a compound in which the EO coefficient increases with concentration even when dispersed or bonded to a medium such as a polymer material at a high concentration. Furthermore, another object of the present invention is to provide a composition comprising the compound, a nonlinear optical element made using the composition, and an optical modulator having the nonlinear optical element and operating based on the electro-optic effect.

[0019] Solution for solving the problem

[0020] The inventors conducted in-depth research and obtained the following insights: compounds with a defined chemical structure can reduce intermolecular interactions and improve dispersibility in a medium. Further research revealed that compounds with a defined chemical structure can be dispersed at high concentrations in media such as polymer materials, and even with increased concentrations, the high EO coefficient continues to increase with the concentration, thus completing this invention.

[0021] That is, the present invention is based on the following principles.

[0022] Scheme 1 of the present invention relates to a compound represented by the following formula (1).

[0023] [Chemical Formula 1]

[0024]

[0025] In formula (1),

[0026] Z 11 The group is represented by the following formula (2).

[0027] Z 12 It is an aromatic group optionally having a substituent or a branched, chain-like or cyclic hydrocarbon group having 1 to 20 carbon atoms optionally having a substituent, said hydrocarbon group optionally being saturated or unsaturated, and a portion of the hydrocarbon chain constituting said hydrocarbon group optionally being substituted by at least one selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms.

[0028] Z 13 It is a divalent aromatic group that optionally has substituents.

[0029] L 11 It is a divalent π-conjugated basis.

[0030] A 11 It is a group represented by formula (6) or formula (7) below.

[0031] Z 12 With Z 13 They can be arbitrarily connected to form a ring structure.

[0032] [Chemical Formula 2]

[0033]

[0034] In formula (2),

[0035] R 21The group is selected from the group consisting of alkyl groups optionally having substituents, aromatic groups optionally having substituents, amino groups optionally having substituents, halogen atoms, arylalkoxy groups optionally having substituents, arylalkyl groups optionally having substituents, alkoxy groups optionally having substituents, alkylthio groups optionally having substituents, arylalkylthio groups optionally having substituents, and silyl groups optionally having substituents.

[0036] Ar 21 The group selected is from the group consisting of aromatic groups, hydrocarbon cyclic groups, and heterocyclic groups, optionally having a group other than R. 21 Other than groups.

[0037] * indicates the bonding position with N in equation (1).

[0038] [Chemical Formula 3]

[0039]

[0040] In formula (6),

[0041] * is the L in equation (1) 11 The bonding positions.

[0042] R 61 and R 62 Each of the groups independently is selected from the group consisting of alkyl groups optionally having substituents, aromatic groups optionally having substituents, halogen atoms, alkyl sulfonyl groups optionally having substituents, and aralkyl groups optionally having substituents.

[0043] X 61 For O or S.

[0044] [Chemical Formula 4]

[0045]

[0046] In formula (7),

[0047] * is the L in equation (1) 11 The bonding positions.

[0048] R 73 The group is selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an aromatic group optionally having a substituent, an acyl group optionally having a substituent, an alkoxycarbonyl group optionally having a substituent, and an aralkyl group optionally having a substituent.

[0049] Scheme 2 of the present invention relates to the compound of Scheme 1, wherein the formula (2) is represented by the following formula (3).

[0050] [Chemical Formula 5]

[0051]

[0052] In formula (3),

[0053] R 31 and R 32 Each independently represents R in equation (2). 21 Groups with the same meaning.

[0054] Ar 33 The group selected is from the group consisting of aromatic groups, hydrocarbon cyclic groups, and heterocyclic groups, optionally having a group other than R. 31 and R 32 Other than groups.

[0055] * indicates the bonding position with N in equation (1).

[0056] Scheme 3 of the present invention relates to a compound of Scheme 1 or 2, wherein Z in formula (1) 12 It is an alkyl group that optionally has substituents or an aromatic group that optionally has substituents.

[0057] Scheme 4 of the present invention relates to a compound of any one of schemes 1 to 3, wherein Z in formula (1) 13 It is a divalent aromatic hydrocarbon group that optionally has substituents.

[0058] Scheme 5 of the present invention relates to a compound of any one of schemes 1 to 4, wherein L in formula (1) 11 It is a group represented by formula (4) or formula (5) below.

[0059] [Chemical Formula 6]

[0060]

[0061] In equation (4),

[0062] R 4a Each of the groups independently consists of a hydrogen atom, an alkyl group optionally having a substituent, an aromatic group optionally having a substituent, an amino group optionally having a substituent, a halogen atom, an alkoxy carbonyl group optionally having a substituent, an alkyl sulfonyl group optionally having a substituent, an aralkyl group optionally having a substituent, an alkoxy group optionally having a substituent, an alkylthio group optionally having a substituent, and an aralkylthio group optionally having a substituent.

[0063] R 4b Each of the groups is independently selected from the group consisting of an alkyl group selected from hydrogen atoms, optionally having substituents, and optionally having substituents, an aromatic group.

[0064] R 4c Each of the groups is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aromatic group optionally having a substituent.

[0065] In addition, R 4a R 4b and R 4c They can be optionally bonded together to form a ring.

[0066] l is an integer from 0 to 5, n is an integer from 0 to 5, m is an integer from 0 to 5, and l + n + m > 0.

[0067] [Chemical Formula 7]

[0068]

[0069] In formula (5),

[0070] Ar 5 Each of these independently represents a divalent aromatic group that optionally has substituents.

[0071] R 5a Each group is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aromatic group optionally having a substituent. Furthermore, in Ar... 5 In the case of substituents, the substituents and R 5a They can be optionally bonded together to form a ring.

[0072] e is an integer from 0 to 4, f is an integer from 0 to 5, and e + f > 0.

[0073] Scheme 6 of the present invention relates to a nonlinear optically active polymer compound, which is formed by bonding a group obtained by removing at least one hydrogen atom from a compound according to any one of Schemes 1 to 5 to a repeating unit in the polymer compound.

[0074] Scheme 7 of the present invention relates to the nonlinear optically active polymer of Scheme 6, wherein the polymer is selected from the group consisting of poly(meth)acrylate, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, polycarbonate, and copolymers thereof.

[0075] Scheme 8 of the present invention relates to a composition comprising at least one of the compounds according to any one of schemes 1 to 5, a polymeric material and a solvent, or comprising at least one of the nonlinear optically active polymeric compounds according to scheme 6 or 7 and a solvent, or comprising at least one of the compounds according to any one of schemes 1 to 5, at least one of the nonlinear optically active polymeric compounds according to scheme 6 or 7 and a solvent.

[0076] Scheme 9 of the present invention relates to the composition of Scheme 8, wherein the polymeric compound is selected from the group consisting of poly(meth)acrylate, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, polycarbonate, and copolymers thereof.

[0077] Scheme 10 of the present invention relates to a nonlinear optical element, which is made using the composition according to Scheme 8 or 9.

[0078] Scheme 11 of the present invention relates to a nonlinear optical element of Scheme 10, wherein the nonlinear optical element operates based on the electro-optic effect.

[0079] Scheme 12 of the present invention relates to an optical modulator having a nonlinear optical element according to scheme 10 or 11.

[0080] Invention Effects

[0081] According to the present invention, a compound is provided in which the EO coefficient increases with its concentration even when dispersed or bonded to a medium such as a polymer material at a high concentration. Detailed Implementation

[0082] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to the following description, and modifications can be made to implement it without departing from the spirit of the invention. It should be noted that in this specification, when “~” is used and numerical values ​​or property values ​​are included before and after it, it is used in a manner that includes the values ​​before and after it.

[0083] (Explanation of terminology)

[0084] The terminology used in this implementation is explained.

[0085] <Substituent>

[0086] Unless otherwise specified, a substituent refers to any group, but is preferably selected from the substituent group G below. 1 The group. Furthermore, the substituents optionally present as described are selected from the substituent group G. 1Or preferably, the substituents are selected from the substituent group G. 1 In the case of substituents, the preferred substituents are also as shown in the following substituent group G. 1 As recorded in the text.

[0087] Substitutional basis set G 1 It is the group consisting of hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, aromatic oxy, alkoxy carbonyl, acyloxy, dialkylamino, aromatic amino, aromatic alkylamino, acyl, halogen atom, haloalkyl, alkylthio, aromatic thio, silyl, silanoxy, cyano, aralkyl, and aromatic groups. These substituents optionally include any of the following structures: straight chain, branched chain, and cyclic.

[0088] The alkyl group has 1 or more carbon atoms, and is usually 24 or less, preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, dodecyl, adamantyl, etc.

[0089] The alkenyl group typically has 2 or more carbon atoms, and typically 24 or fewer, preferably 12 or fewer, and more preferably 6 or fewer, and is either straight-chain, branched, or cyclic. Specific examples include vinyl groups.

[0090] The alkynyl group is typically a straight-chain or branched group with 2 or more carbon atoms, and typically 24 or less, preferably 12 or less, and more preferably 6 or less. Specific examples include acetylene groups.

[0091] The alkoxy group has 1 or more carbon atoms, and is usually 24 or less, preferably 12 or less, and more preferably 6 or less; it is a straight-chain, branched, or cyclic alkoxy group. Specific examples include methoxy and ethoxy groups.

[0092] The aromatic oxygen group has 4 or more carbon atoms, preferably 5 or more, and usually 36 or less, preferably 24 or less, and more preferably 10 or less. Specific examples include phenoxy, naphthoxy, and phenylsulfoxy groups.

[0093] The carbonyl group has 2 or more carbon atoms, and is usually 24 or less, preferably 12 or less, and more preferably 7 or less. Specific examples include methoxycarbonyl and ethoxycarbonyl.

[0094] Acyloxy groups having 2 or more carbon atoms, typically 24 or fewer, preferably 12 or fewer, and more preferably 7 or fewer. Specific examples include acetoxy, propionyloxy, and benzoyloxy.

[0095] The dialkylamino group has 2 or more carbon atoms, and is typically 24 or less, preferably 12 or less, and more preferably 6 or less. Specific examples include dimethylamino, diethylamino, ethylmethylamino, and isopropylamino.

[0096] The aromatic amino group has 10 or more carbon atoms, preferably 12 or more, and usually 36 or less, preferably 24 or less, and more preferably 14 or less. Specific examples include diphenylamino, xylylamino, and N-carbazole.

[0097] Aromatic amino groups with 7 or more carbon atoms, typically 36 or fewer, preferably 24 or fewer, and more preferably 8 or fewer, are aromatic alkyl amino groups. Specific examples include benzylamino.

[0098] The acyl group has 2 or more carbon atoms, and is usually 24 or less, preferably 12 or less, and more preferably 7 or less. Specific examples include acetyl and benzoyl groups.

[0099] Halogen atoms such as fluorine, chlorine, bromine, and iodine. Fluorine atoms are preferred.

[0100] The alkyl halogroup has 1 or more carbon atoms, and is usually 12 or less, preferably 6 or less. Specific examples include trifluoromethyl.

[0101] The alkylthio group has 1 or more carbon atoms, and is usually 24 or less, preferably 12 or less, and more preferably 6 or less. Specific examples include methylthio and ethylthio.

[0102] The aromatic thio group has 4 or more carbon atoms, preferably 5 or more, and usually 36 or less, preferably 24 or less, and more preferably 10 or less. Specifically, examples include phenylthio and naphthio.

[0103] The silane group typically has 2 or more carbon atoms, preferably 3 or more, and typically 36 or less, preferably 24 or less, and more preferably 18 or less. Specific examples include trimethylsilane, tert-butyldimethylsilane, tert-butyldiphenylsilane, and triphenylsilane.

[0104] The silanoxy group has 2 or more carbon atoms, preferably 3 or more, and usually 36 or less, preferably 24 or less, and more preferably 18 or less. Specific examples include trimethylsilanoxy, tert-butyldimethylsilanoxy, tert-butyldiphenylsilanoxy, and triphenylsilanoxy.

[0105] Araneyl 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, 2-phenylethyl, 2-phenylpropyl-2-yl, 2-phenylbutyl-2-yl, 3-phenylpentyl-3-yl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, 7-phenyl-1-heptyl, 8-phenyl-1-octyl, etc.

[0106] Aromatic groups having 6 or more carbon atoms, typically 36 or fewer, and preferably 24 or fewer. Specific examples include: phenyl, naphthyl, groups formed by multiple phenyl groups, thiophene, furanyl, pyridyl, etc.

[0107] The substituents may optionally include any of the following structures: straight chain, branched chain, or cyclic.

[0108] When the substituents are adjacent, the adjacent substituents may optionally bond to each other to form a ring. Preferred ring sizes are 4-membered, 5-membered, and 6-membered rings. Specific examples include cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0109] <alkyl>

[0110] The alkyl group optionally has substituents, optionally being straight-chain, branched, or cyclic. Generally, the number of carbon atoms is not limited, but is preferably 1 to 50 carbon atoms, with 30 or fewer carbon atoms being a more preferable upper limit, and 10 or fewer carbon atoms being even more preferable. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, dodecyl, adamantyl, etc.

[0111] These groups optionally have substituents selected from the substituent group G. 1 .

[0112] <Aromatic Groups>

[0113] The aromatic group may optionally have substituents, representing aromatic hydrocarbon groups or aromatic heterocyclic groups, which, depending on the bonding state in the structure of the compound to be described later, refer to a monovalent, divalent, or trivalent or higher structure.

[0114] In the structure of aromatic hydrocarbon groups, the number of carbon atoms is generally not limited, but it is preferred to have 6 or more and 60 or less carbon atoms. As an upper limit for the number of carbon atoms, it is more preferably 48 or less carbon atoms, and even more preferably 30 or less carbon atoms. Specifically, examples include: single rings of 6-membered rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetraphenylene ring, pyrene ring, benzo[a]pyrene ring, cyclopentadiene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc., or condensed cyclic groups containing 2 to 5 rings, or structures formed by connecting multiple groups selected from these. When multiple aromatic hydrocarbon groups are connected, structures formed by connecting 2 to 10 groups are generally listed, and structures formed by connecting 2 to 5 groups are preferred.

[0115] When multiple aromatic hydrocarbon groups are connected, they can be connected in the same structure or in different structures.

[0116] In the structure of aromatic heterocyclic groups, there is usually no limitation on the number of carbon atoms, but it is preferred to have 3 or more and 50 or less carbon atoms as the upper limit of the number of carbon atoms, more preferably 45 or less carbon atoms, and even more preferably 30 or less carbon atoms. Specifically, examples include: 5- to 6-membered rings such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazol ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thiophenolopyrrole ring, thiophenolothiophene ring, furanolopyrrole ring, furanolofuran ring, thiophenolofuran ring, benzoisoxazole ring, benzoisothiazol ring, benzoimidazol ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, borazolin ring, quinoxaline ring, phenanthridine ring, naphthalene-intercalated diazabenzene ring, quinazoline ring, quinazoline ring, quinazoline ketone ring, etc., monocyclic rings or condensed cyclic groups containing 2 to 4 rings, or groups formed by connecting multiple of them. When multiple aromatic heterocyclic groups are connected, they can be connected in the same structure or in different structures. When multiple aromatic heterocyclic groups are connected, structures consisting of 2 to 10 groups can be listed, with structures consisting of 2 to 5 groups being preferred.

[0117] These groups optionally have substituents selected from the substituent group G. 1 .

[0118] <Amino>

[0119] The amino group optionally has substituents, preferably secondary or tertiary amino groups, more preferably tertiary amino groups. As substituents of the amino group, alkyl, cycloalkyl, and aromatic groups are preferred, and these groups optionally have substituents. In the case of dialkylamino groups, the number of carbon atoms is 2 or more, usually 24 or less, preferably 12 or less, more preferably 6 or less. Specific examples include: dimethylamino, diethylamino, ethylmethylamino, n-propylmethylamino, di-n-butylamino, di-n-hexylamino, diisopropylamino, etc.

[0120] In the case of aromatic amino groups, the number of carbon atoms is 10 or more, preferably 12 or more, typically 36 or less, preferably 24 or less, and more preferably 14 or less. Specific examples include diphenylamino, xylylamino, and N-carbazole.

[0121] In the case of aromatic alkylamino groups, the aromatic amino group has 7 or more carbon atoms, and is generally 36 or less, preferably 24 or less, and more preferably 8 or less. Specific examples include benzylamino.

[0122] Furthermore, when there are multiple substituents present in the amino group, they may be identical or different, and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded.

[0123] These groups optionally have substituents selected from the substituent group G. 1 .

[0124] <halogen atom>

[0125] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0126] <alkoxycarbonyl>

[0127] The alkoxycarbonyl group optionally has substituents. Generally, the number of carbon atoms is not limited, but it is preferably 2 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 30 or less, and even more preferably 20 or less. Specific examples include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-hexyloxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, etc.

[0128] These groups optionally have substituents selected from the substituent group G. 1 .

[0129] <acyl>

[0130] The acyl group optionally has substituents. Generally, there is no limitation on the number of carbon atoms, but it is preferred to have 2 or more and 50 or less carbon atoms. As an upper limit for the number of carbon atoms, it is more preferably 24 or less carbon atoms, and even more preferably 12 or less carbon atoms. Specific examples include benzoyl and acetyl groups.

[0131] These groups optionally have substituents selected from the substituent group G. 1 .

[0132] <alkylsulfonyl>

[0133] The alkylsulfonyl group optionally has substituents. Generally, the number of carbon atoms is not limited, but it is preferably 2 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 30 or less, and even more preferably 20 or less. Specific examples include: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, n-hexylsulfonyl, cyclohexylsulfonyl, dodecylsulfonyl, etc.

[0134] These groups optionally have substituents selected from the substituent group G. 1 .

[0135] <Aryl>

[0136] The aralkyl group optionally has substituents. Generally, there is no limitation on the number of carbon atoms, but it is preferred to have 4 or more and 50 or less carbon atoms. As an upper limit for the number of carbon atoms, it is more preferably 30 or less carbon atoms, and even more preferably 20 or less carbon atoms. Specific examples include: benzyl, tolylmethyl, thienylmethyl, 2-phenylethyl, 2-phenylpropyl-2-yl, 2-phenylbutyl-2-yl, 3-phenylpentyl-3-yl, 3-phenyl-1-propyl, 4-phenyl-1-butyl, 5-phenyl-1-pentyl, 6-phenyl-1-hexyl, 7-phenyl-1-heptyl, 8-phenyl-1-octyl, etc.

[0137] These groups optionally have substituents selected from the substituent group G. 1 .

[0138] <Aromatic oxygen>

[0139] The aromatic oxygen group optionally has substituents. Generally, there is no limitation on the number of carbon atoms, but it is preferably 3 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 30 or less, and even more preferably 20 or less. Specific examples include naphthoxy and phenylthiooxy.

[0140] These groups optionally have substituents selected from the substituent group G. 1 .

[0141] <Arylalkoxy>

[0142] The arylalkoxy group optionally has substituents. Generally, the number of carbon atoms is not limited, but it is preferably 4 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 30 or less, and even more preferably 20 or less. Specific examples include: benzyloxy, tolylmethoxy, thiophenemethoxy, 2-phenylethoxy, 2-phenylpropyl-2-yloxy, 2-phenylbutyl-2-yloxy, 3-phenylpentyl-3-yloxy, 3-phenyl-1-propoxy, 4-phenyl-1-butoxy, 5-phenyl-1-pentoxy, 6-phenyl-1-hexyloxy, 7-phenyl-1-heptoxy, 8-phenyl-1-octoxy, etc.

[0143] These groups optionally have substituents selected from the substituent group G. 1 .

[0144] <alkoxy>

[0145] The alkoxy group optionally has substituents. Generally, the number of carbon atoms is not limited, but it is preferably 1 to 50 carbon atoms. As an upper limit for the number of carbon atoms, it is more preferably 20 or less, and even more preferably 10 or less. Specific examples include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, dodecyloxy, etc.

[0146] These groups optionally have substituents selected from the substituent group G. 1 .

[0147] <alkylthio>

[0148] The alkylthio group optionally has substituents. Generally, the number of carbon atoms is not limited, but it is preferably 1 to 50 carbon atoms. As an upper limit for the number of carbon atoms, it is more preferably 20 or less, and even more preferably 10 or less. Specific examples include: methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-hexylthio, cyclohexylthio, dodecylthio, etc.

[0149] These groups optionally have substituents selected from the substituent group G. 1 .

[0150] <Aromatic sulfhydryl>

[0151] The aromatic thio group optionally has substituents. Generally, there is no limitation on the number of carbon atoms, but it is preferably 3 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 30 or less, and even more preferably 20 or less. Specific examples include benzylthio, toluenethio, and phenylthiothio.

[0152] These groups optionally have substituents selected from the substituent group G. 1 .

[0153] <Aranethio>

[0154] The arylalkoxy group optionally has substituents. Generally, the number of carbon atoms is not limited, but it is preferably 4 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 30 or less, and even more preferably 20 or less. Specific examples include: benzylthio, tolylmethylthio, 2-phenylethylthio, 2-phenylpropyl-2-ylthio, 2-phenylbutyl-2-ylthio, 3-phenylpentyl-3-ylthio, 3-phenyl-1-propanethio, 4-phenyl-1-butylthio, 5-phenyl-1-pentylthio, 6-phenyl-1-hexylthio, 7-phenyl-1-heptylthio, 8-phenyl-1-octylthio, etc.

[0155] These groups optionally have substituents selected from the substituent group G. 1 .

[0156] <Silyl>

[0157] The silane group optionally has substituents. Generally, there is no limitation on the number of carbon atoms, but it is preferably 3 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 20 or less, and even more preferably 10 or less. Specific examples include trimethylsilane, triethylsilane, propyl dimethylsilane, tert-butyl dimethylsilane, and tert-butyl diphenylsilane.

[0158] These groups optionally have substituents selected from the substituent group G. 1 .

[0159] <Hydrocyclo group>

[0160] The hydrocarbon cyclic group is a cyclic hydrocarbon group, optionally having substituents. Generally, there is no limitation on the number of carbon atoms, but it is preferably 3 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 20 or less, and even more preferably 10 or less. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or groups formed by connecting multiple of them.

[0161] These groups optionally have substituents selected from the substituent group G. 1 .

[0162] <heterocyclic group>

[0163] The heterocyclic group optionally has substituents. Generally, the number of carbon atoms is not limited, but it is preferably 3 or more and 50 or less. As an upper limit for the number of carbon atoms, it is more preferably 20 or less, and even more preferably 10 or less. Specific examples include: thiaalkyl, 1,4-dithiaalkyl, tetrahydrofuranyl, tetrahydropyranyl, pyranyl, 1,4-dioxaneyl, or groups formed by connecting multiple of them.

[0164] These groups optionally have substituents selected from the substituent group G. 1 .

[0165] <A branched, chain, or cyclic saturated or unsaturated hydrocarbon chain, wherein a portion of its carbon atoms are optionally substituted with oxygen, sulfur, and / or silicon atoms>

[0166] A group consisting of a branched, chain-like, or cyclic saturated or unsaturated hydrocarbon chain, wherein a portion of its carbon atoms are optionally substituted with oxygen, sulfur, and / or silicon atoms, refers to a group consisting of a carbon chain composed of alkyl, alkenyl, or alkynyl groups on branches of 1 to 20 carbon atoms, wherein a portion of the chain is optionally substituted with oxygen, sulfur, and / or silicon atoms. These groups may optionally have substituents.

[0167] Specifically, the following groups can be listed.

[0168] Specific examples of unsubstituted hydrocarbon chains are 1 to 20, and more specifically, examples include: methyl, ethyl, 1-butyl, tert-butyl, cyclopentyl, 4-ethyl-1-cyclohexyl, 2-penten-1-yl, 1-octyl, 1-decyl, etc., with methyl, ethyl, and 1-butyl being preferred.

[0169] Specific examples of the substitution of oxygen atoms include 2-ethoxyethyl, 2-(2-ethoxyethoxy)ethyl, 2-hydroxyethyl, tetrahydropyranoxypropyl, etc., with 2-ethoxyethyl and 2-hydroxyethyl being preferred, and 2-hydroxyethyl being particularly preferred.

[0170] Specific examples of sulfur atoms being substituted include: 2-ethylthioethyl, tetrahydrothiophene, 2-(2-ethylthioethylthio)ethyl, etc.

[0171] Specific examples of silicon atoms being substituted include trimethylsilyl, tert-butyldimethylsilyl, etc.

[0172] Furthermore, they may optionally be substituted simultaneously with oxygen atoms and silicon atoms. Specific examples include 2-(trimethylsilyloxy)ethyl, 2-(tert-butyldimethylsilyloxy)ethyl, 4-(tert-butyldimethylsilyloxy)butyl, 2-(tert-butyldiphenylsilyloxy)ethyl, 2-(tert-butyldimethylsilyloxy)hexyl, etc., with 2-(tert-butyldimethylsilyloxy)ethyl and 4-(tert-butyldimethylsilyloxy)butyl being preferred.

[0173] These groups optionally have substituents selected from the substituent group G. 1 .

[0174] <π conjugation base>

[0175] A π-conjugated group is a group consisting of alternating single and multiple bonds and possessing delocalized electrons (π electrons). The π-conjugated group optionally has substituents; generally, the number of carbon atoms is not limited, but preferably 2 to 50 carbon atoms, more preferably 30 or less, and even more preferably 20 or less. Furthermore, the substituents of multiple π-conjugated groups can optionally bond together to form a cyclic structure. Specific examples include vinylidene, thiophene, furanyl, and pyrroleyl groups.

[0176] These groups optionally have substituents selected from the substituent group G. 1 .

[0177] <Terminated isocyanate group>

[0178] The terminator isocyanate group refers to a group in which the isocyanate group is protected by a terminator. It is characterized by its stability under normal conditions and the regeneration of the isocyanate group by dissociation of the terminator through heat treatment. The choice of the terminator group is not particularly limited, but the number of carbon atoms is 1 to 50, with 30 or fewer carbon atoms being the upper limit, and 20 or fewer carbon atoms being even more preferred. Furthermore, the substituents of the plurality of π-conjugated groups are optionally bonded to form a cyclic structure. Specific examples include methylethyl oxime, 3,5-dimethylpyrazolyl, and ε-caprolactam. Dimethylpyrazolyl is preferred.

[0179] The heat treatment temperature required for the dissociation of the capping agent varies depending on the catalyst and reaction conditions, and is therefore not particularly limited, typically ranging from 20°C to 250°C. The lower limit is preferably 40°C or higher, more preferably 60°C or higher, most preferably 100°C or higher, and the upper limit is preferably 250°C or lower, more preferably 200°C or lower.

[0180] <π-conjugated electron-withdrawing groups>

[0181] A π-conjugated electron-withdrawing group refers to a group consisting of alternating single and multiple bonds and possessing delocalized electrons (π electrons), indicating a group having one or more electron-withdrawing groups as substituents. Generally, the number of carbon atoms is not limited, but preferably 2 to 30 carbon atoms, with an upper limit of 10 carbon atoms or less, and even more preferably 6 carbon atoms or less. Furthermore, the substituents of multiple π-conjugated groups can optionally bond together to form a cyclic structure, resulting in high amorphousness and high chemical stability; therefore, electron-withdrawing π-conjugated groups containing cyclic structures are more preferred. Specific examples of electron-withdrawing groups include nitro, cyano, alkyl carbonyl, or alkoxy carbonyl, with cyano being more preferred.

[0182] <Polymers>

[0183] In this specification, "polymer compound" refers to a compound with a molecular weight of 2000 or more and containing four or more identical repeating units in its molecule. There are no particular limitations on the polymer compound; it is preferably a polymer, which can be any of a homopolymer, block copolymer, random copolymer, alternating copolymer, or graft copolymer, or other forms.

[0184] <Dendrolytic compounds>

[0185] In this specification, a dendritic compound refers to a compound having a structure that branches regularly from the center, and means a compound with a carbon number preferably of 6 or more and 84 or less, more preferably 8 or more, more preferably 57 or less, further preferably 49 or less, and particularly preferably 25 or less.

[0186] The dendritic compounds mentioned in this specification do not include compounds equivalent to the aforementioned polymers.

[0187] As preferred specific examples of dendritic compounds in this specification, compounds represented by general formula A or general formula B are listed below.

[0188] [Chemical Formula 8]

[0189]

[0190] (In the above general formulas A and B, * represents the bonding position with the compound shown in formula (1).)

[0191] D 1 ~D 10 Each of these groups independently represents a divalent linker that optionally has substituents and is optionally bonded to any position on the benzene ring.

[0192] E 1 ~E 42 Each group independently represents a monovalent group and is optionally bonded to any position on the benzene ring.

[0193] As D 1 ~D 10 Preferably, each is an alkylene group, ester group, ether group or an alkyl ether group having 1 to 5 carbon atoms. From the viewpoint of compound stability, it is more preferably an alkylene group, ester group or an ether group having 1 to 2 carbon atoms.

[0194] As E 1 ~E 42 Preferably, each of the following groups is independently selected from the group consisting of hydrogen atom, hydroxyl group, optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted alkoxy group, optionally substituted aromatic oxy group, optionally substituted alkoxy carbonyl group, optionally substituted acyloxy group, optionally substituted dialkylamino group, optionally substituted aromatic amino group, optionally substituted aromatic alkylamino group, optionally substituted acyl group, halogen atom, optionally substituted alkylthio group, optionally substituted aromatic thio group, optionally substituted silyl group, optionally substituted silylalkoxy group, cyano group, optionally substituted aralkyl group, and optionally substituted aromatic group, more preferably substituted acyl group, optionally substituted aralkyl group, hydrogen atom or fluorine atom, and even more preferably hydrogen atom or fluorine atom.

[0195] As an optional substituent, it is preferably an alkyl or fluorine atom having 1 to 5 carbon atoms.

[0196] <The compound shown in formula (1)>

[0197] The compound in this embodiment is represented by the following formula (1).

[0198] [Chemical Formula 9]

[0199]

[0200] In formula (1),

[0201] Z 11 The group is represented by the following formula (2).

[0202] Z 12 It is an aromatic group optionally having a substituent or a branched, chain-like or cyclic hydrocarbon group having 1 to 20 carbon atoms optionally having a substituent, said hydrocarbon group optionally being saturated or unsaturated, and a portion of the hydrocarbon chain constituting said hydrocarbon group optionally being substituted by at least one selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms.

[0203] Z 13It is a divalent aromatic group that optionally has substituents.

[0204] L 11 It is a divalent π-conjugated basis.

[0205] A 11 It is a group represented by formula (6) or formula (7) below.

[0206] Z 12 With Z 13 They can be arbitrarily connected to form a ring structure.

[0207] [Chemical Formula 10]

[0208]

[0209] In formula (2),

[0210] R 21 The group is selected from the group consisting of alkyl groups optionally having substituents, aromatic groups optionally having substituents, amino groups optionally having substituents, halogen atoms, arylalkoxy groups optionally having substituents, arylalkyl groups optionally having substituents, alkoxy groups optionally having substituents, alkylthio groups optionally having substituents, arylalkylthio groups optionally having substituents, and silyl groups optionally having substituents.

[0211] Ar 21 The group selected is from the group consisting of aromatic groups, hydrocarbon cyclic groups, and heterocyclic groups, optionally having a group other than R. 21 Other than groups.

[0212] * indicates the bonding position with N in equation (1).

[0213] [Z] 11 ]

[0214] Z 11 The group is represented by the formula (2).

[0215] Z 11 The neighboring position of the "*" indicating the bonding position with N in equation (1) has R, which will be described later. 21 The compound shown in formula (1) is obtained through Z. 11 With R 21 And become Z 11 and Z 13 Structures not on the same plane become large in molecular structure, thus inhibiting the aggregation of compounds. Therefore, it is believed that the compound shown in formula (1) can be dispersed or bonded in polymer materials and other media at high concentrations, and can obtain a high EO coefficient even in the state of high concentration dispersion or bonding.

[0216] (R)21 )

[0217] R 21 The group is selected from the group consisting of alkyl groups optionally having substituents, aromatic groups optionally having substituents, amino groups optionally having substituents, halogen atoms, arylalkoxy groups optionally having substituents, arylalkyl groups optionally having substituents, alkoxy groups optionally having substituents, alkylthio groups optionally having substituents, arylalkylthio groups optionally having substituents, and silyl groups optionally having substituents.

[0218] As R 21 Among the selected groups, from the viewpoint of improving nonlinear optical effects, alkyl groups optionally having substituents, alkoxy groups optionally having substituents, aralkoxy groups optionally having substituents, aralkyl groups optionally having substituents, alkylthio groups optionally having substituents, aromatic groups optionally having substituents, and silyl groups optionally having substituents are preferred from the viewpoint of compound stability. Furthermore, alkyl groups optionally having substituents and alkoxy groups optionally having substituents are more preferred, and alkyl groups optionally having substituents are most preferred.

[0219] More preferred examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, and dodecyl; more preferably: methyl, ethyl, n-propyl, isopropyl, and n-hexyl; and most preferably: methyl and ethyl.

[0220] More preferred specific examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, dodecyloxy, with the most preferred examples being: methoxy, ethoxy, isopropoxy, and n-hexyloxy.

[0221] R 21 The optional substituents are preferably selected from the substituent group G. 1 From the viewpoint of compound stability, more preferred specific examples include: hydroxyl, alkoxy, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, halogen atom, silyl group, silanoxy; even more preferred examples include: halogen atom, hydroxyl, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, silyl group, silanoxy; and most preferred examples include: hydroxyl, silanoxy.

[0222] (Ar) 21 )

[0223] Ar 21The group selected is from the group consisting of aromatic groups, hydrocarbon cyclic groups, and heterocyclic groups, optionally having a group other than R. 21 Other than these groups. Among these, aromatic groups and hydrocarbon cyclic groups are more preferred, and aromatic groups are most preferred.

[0224] As Ar 21 Preferred examples of the selected aromatic groups include: benzene ring, furan ring, thiophene ring, more preferably: benzene ring, thiophene ring, and most preferably benzene ring.

[0225] As Ar 21 Preferred examples of the selected hydrocarbon cyclic group include cyclopentyl, cyclohexyl, and cycloheptyl, with cyclohexyl being the most preferred.

[0226] Ar 21 The optional substituents are preferably alkyl groups, aromatic groups, amino groups, halogen atoms, arylalkoxy groups, alkoxy groups, alkylthio groups, or arylalkoxy groups. From the viewpoint that higher electron-donating properties result in a higher EO coefficient, more preferably, the following groups are listed: alkyl groups, amino groups, arylalkyl groups, alkoxy groups, alkoxy groups, alkoxy groups, arylalkoxy groups, and arylalkoxy groups. More preferably, the following groups are listed: arylalkoxy groups, alkyl groups, amino groups, and alkoxy groups. Most preferably, alkyl, amino, and alkoxy groups are listed.

[0227] More preferred specific examples of amino groups include: dimethylamino, diethylamino, ethylmethylamino, n-propylmethylamino, diisopropylamino, di-n-butylamino, and di-n-hexylamino. More preferably, examples include: ethylmethylamino, di-n-butylamino, methylphenylamino, ethylphenylamino, butylphenylamino, hexylphenylamino, diphenylamino, 2,6-dimethylphenylphenylamino, and 2,4,6-trimethylphenylphenylamino.

[0228] More preferred specific examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, dodecyloxy, with the most preferred examples being: methoxy, ethoxy, isopropoxy, and n-hexyloxy.

[0229] In Ar 21 In cases where the optional substituents further have substituents, the optional substituents are preferably selected from the substituent group G.1 From the viewpoint of compound stability, more preferred specific examples include: hydroxyl, alkoxy, acyloxy, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, halogen atom, silyl group, silanoxy; more preferably: halogen atom, hydroxyl, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, silyl group, silanoxy; and most preferably: hydroxyl, acyloxy, silanoxy.

[0230] From the perspective of further inhibiting the aggregation of the compounds represented by formula (1), formula (2) is more preferably represented by the following formula (3).

[0231] [Chemical Formula 11]

[0232]

[0233] In formula (3),

[0234] R 31 and R 32 Each independently represents R in equation (2). 21 Groups with the same meaning.

[0235] Ar 33 The group selected is from the group consisting of aromatic groups, hydrocarbon cyclic groups, and heterocyclic groups, optionally having a group other than R. 31 and R 32 Other than groups.

[0236] * indicates the bonding position with N in equation (1).

[0237] (R) 31 R 32 )

[0238] R 31 and R 32 Each independently represents R in equation (2). 21 Groups with the same meaning. R 31 and R 32 The preferred solution and for R in equation (2) 21 The scope is the same.

[0239] (Ar) 33 )

[0240] Ar 33 The group selected is from the group consisting of aromatic groups, hydrocarbon cyclic groups, and heterocyclic groups, optionally having a group other than R. 31 and R 32 Other groups besides Ar. 33 The preferred solution and Ar in equation (2) 21The scope is the same.

[0241] [Z] 12 ]

[0242] Z 12 It is an aromatic group optionally having a substituent or a branched, chain-like or cyclic hydrocarbon group having 1 to 20 carbon atoms optionally having a substituent, said hydrocarbon group optionally being saturated or unsaturated, and a portion of the hydrocarbon chain constituting said hydrocarbon group optionally being substituted by at least one selected from oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms.

[0243] From the perspective of compound stability, Z 12 Preferably, it is an alkyl group that optionally has a substituent or an aromatic group that optionally has a substituent, more preferably an aromatic group that optionally has a substituent.

[0244] In Z 12 In this process, a portion of the hydrocarbon chain constituting the hydrocarbon group is optionally substituted by at least one selected from oxygen, sulfur, nitrogen and silicon atoms.

[0245] In Z 12 In the case where a portion of the hydrocarbon chain constituting the hydrocarbon group is substituted, it is preferably substituted by at least one selected from oxygen atoms, sulfur atoms, and silicon atoms.

[0246] Here, "part of a hydrocarbon chain" means at least one methylene, methine, or carbon atom contained in the hydrocarbon chain. For example, the methylene in the hydrocarbon chain may optionally be replaced by an oxygen atom or a sulfur atom to become -O- or -S-, the methine in the hydrocarbon chain may optionally be replaced by a nitrogen atom to become -NH-, and the carbon atom in the hydrocarbon chain may optionally be replaced by a silicon atom to become -SiH2-.

[0247] As Z 12 More preferred examples of the selected aromatic group include: benzene ring, biphenyl ring, furan ring, thiophene ring, and even more preferred examples include: benzene ring, biphenyl ring, thiophene ring, and most preferably benzene ring.

[0248] As Z 12 More preferred examples of groups consisting of branched, chain-like, or cyclic saturated or unsaturated hydrocarbon chains with 1 to 20 carbon atoms, wherein a portion of the carbon atoms are optionally substituted by oxygen, sulfur, nitrogen, and / or silicon atoms, include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, thiacyclohexyl, 1,4-dithiaalkyl, tetrahydrofuranyl, tetrahydropyranyl, pyranyl, and 1,4-dioxylalkyl.

[0249] Z 12Optionally, the substituents may be alkyl groups, aromatic groups, amino groups, halogen atoms, alkoxy carbonyl groups, alkyl sulfonyl groups, aralkyl groups, alkoxy groups, alkthio groups, aralkyl thio groups, or acyl groups. From the viewpoint that higher electron permissibility leads to a higher EO coefficient, it is more preferable to have alkyl groups, amino groups, aralkyl groups, alkoxy groups, alkthio groups, or aralkyl thio groups; further preferably, alkyl groups, amino groups, or alkoxy groups; and most preferably, amino groups or alkoxy groups.

[0250] More preferred examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, dodecyl, and more preferably: methyl, ethyl, n-propyl, n-hexyloxy, and most preferably: methyl, ethyl.

[0251] More preferred specific examples of amino groups include: dimethylamino, diethylamino, ethylmethylamino, n-propylmethylamino, diisopropylamino, di-n-butylamino, and di-n-hexylamino. Further preferred examples include: ethylmethylamino, di-n-butylamino, methylphenylamino, ethylphenylamino, butylphenylamino, hexylphenylamino, diphenylamino, 2,6-dimethylphenylphenylamino, and 2,4,6-trimethylphenylphenylamino. Particularly preferred are methylphenylamino, ethylphenylamino, butylphenylamino, hexylphenylamino, diphenylamino, 2,6-dimethylphenylphenylamino, and 2,4,6-trimethylphenylphenylamino. Most preferred are methylphenylamino, ethylphenylamino, butylphenylamino, and hexylphenylamino.

[0252] More preferred specific examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, dodecyloxy, with the most preferred examples being: methoxy, ethoxy, isopropoxy, and n-hexyloxy.

[0253] In Z 12 In cases where the optional substituents further have substituents, preferably the optional substituents are selected from the substituent group G. 1From the viewpoint of compound stability, more preferred specific examples include: hydroxyl, alkoxy, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, halogen atom, silyl group, silanoxy, acyloxy, and hydroxyl group. More preferably examples include: halogen atom, hydroxyl, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, silyl group, silanoxy, and silanoxy. Most preferably examples include: hydroxyl, acyloxy, and silanoxy.

[0254] [Z] 13 ]

[0255] Z 13 Z is a divalent aromatic group that optionally has substituents. 13 More preferably, it is a divalent aromatic hydrocarbon group optionally having a substituent. 12 With Z 13 They can be arbitrarily connected to form a ring structure.

[0256] As Z 13 Among the selected aromatic groups, more preferred examples include: benzene ring, naphthyl ring, anthracene ring, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, and thiophene-thiophene ring; more preferably, benzene ring and thiophene ring are listed; and most preferably, benzene ring is listed.

[0257] Z 13 The optional substituents are preferably alkyl groups, aromatic groups, amino groups, halogen atoms, alkoxy carbonyl groups, acyloxy groups, alkyl sulfonyl groups, aralkyl groups, alkoxy groups, or arylalkoxy groups. From the viewpoint of compound stability, alkyl groups, halogen atoms, alkoxy groups, or arylalkoxy groups are more preferred, and alkoxy groups are most preferred.

[0258] More preferred specific examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, dodecyloxy, with the most preferred examples being: methoxy, ethoxy, isopropoxy, and n-hexyloxy.

[0259] More preferred examples of arylalkoxy groups include benzyloxy, tolylmethoxy, 2-phenylethoxy, 2-phenylpropyl-2-yloxy, 2-phenylbutyl-2-yloxy, 3-phenylpentyl-3-yloxy, 3-phenyl-1-propoxy, 4-phenyl-1-butoxy, 5-phenyl-1-pentoxy, 6-phenyl-1-hexyloxy, etc., with benzyl being the most preferred.

[0260] In Z 13 In cases where the optional substituents further have substituents, preferably the optional substituents are selected from the substituent group G. 1 From the viewpoint of compound stability, more preferred specific examples include: hydroxyl, alkoxy, acyloxy, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, halogen atom, silyl group, silanoxy group, and aromatic group. More preferably examples include: halogen atom, hydroxyl, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, silyl group, and silanoxy group. Most preferably examples include: hydroxyl, acyloxy, and silanoxy group.

[0261] [L] 11 ]

[0262] L 11 It is a divalent π-conjugated group. More preferably, it is a group represented by formula (4) or formula (5) below.

[0263] [Chemical Formula 12]

[0264]

[0265] In equation (4),

[0266] R 4a Each of the groups independently consists of a hydrogen atom, an alkyl group optionally having a substituent, an aromatic group optionally having a substituent, an amino group optionally having a substituent, a halogen atom, an alkoxy carbonyl group optionally having a substituent, an alkyl sulfonyl group optionally having a substituent, an aralkyl group optionally having a substituent, an alkoxy group optionally having a substituent, an alkylthio group optionally having a substituent, and an aralkylthio group optionally having a substituent.

[0267] R 4b Each of the groups is independently selected from the group consisting of an alkyl group selected from hydrogen atoms, optionally having substituents, and optionally having substituents, an aromatic group.

[0268] R 4c Each of the groups is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aromatic group optionally having a substituent.

[0269] In addition, R 4a R 4b and R 4c They can be optionally bonded together to form a ring.

[0270] l is an integer from 0 to 5, n is an integer from 0 to 5, m is an integer from 0 to 5, and l + n + m > 0.

[0271] l is an integer from 0 to 5, n is an integer from 0 to 5, m is an integer from 0 to 5, and l + n + m > 0. l is preferably 0 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 1. n is preferably 0 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 1. m is preferably 0 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 1.

[0272] (R) 4a )

[0273] R 4a Each of the groups independently consists of a hydrogen atom, an alkyl group optionally having a substituent, an aromatic group optionally having a substituent, an amino group optionally having a substituent, a halogen atom, an alkoxy carbonyl group optionally having a substituent, an alkyl sulfonyl group optionally having a substituent, an aralkyl group optionally having a substituent, an alkoxy group optionally having a substituent, an alkylthio group optionally having a substituent, and an aralkylthio group optionally having a substituent.

[0274] In which can be R 4a From the viewpoint of compound stability and inhibition of aggregation, the selected groups are more preferably alkyl groups, aromatic groups, halogen atoms, aralkyl groups, alkoxy groups, alkylthio groups, and aralkylthio groups that are optionally substituted, and even more preferably alkyl groups, aralkyl groups, alkoxy groups, alkoxy groups, alkylthio groups, and aralkylthio groups that are optionally substituted, and most preferably alkoxy groups and alkylthio groups that are optionally substituted.

[0275] More preferred specific examples of alkylthio groups include: methylthio, ethylthio, n-propylthio, n-butylthio, isobutylthio, and n-hexylthio, with the most preferred examples being: methylthio, ethylthio, n-propylthio, n-butylthio, and n-hexylthio.

[0276] More preferred specific examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, n-butoxy, isobutoxy, and n-hexyloxy, with the most preferred examples being: methoxy, ethoxy, isopropoxy, and n-hexyloxy.

[0277] (R) 4b )

[0278] R 4b Each of the groups is independently selected from the group consisting of an alkyl group selected from hydrogen atoms, optionally having substituents, and optionally having substituents, an aromatic group.

[0279] In which can be R 4b Among the selected groups, more preferably are: hydrogen atoms, alkyl groups optionally having substituents, and most preferably alkyl groups optionally having substituents.

[0280] More preferred examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, and dodecyl. More preferably, methyl, ethyl, n-propyl, isopropyl, and n-hexyl are listed. Most preferably, methyl, ethyl, n-propyl, and n-hexyl are listed.

[0281] (R) 4c )

[0282] R 4c Each of the groups is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aromatic group optionally having a substituent.

[0283] In which can be R 4c Among the selected groups, alkyl groups optionally having substituents, hydrogen atoms, alkoxy groups optionally having substituents, and hydrogen atoms are more preferred.

[0284] These R 4a R 4b R 4c The optional substituents are preferably selected from the substituent group G. 1 From the viewpoint of compound stability, more preferred examples of substituents are hydroxyl, alkoxy, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, halogen atom, silyl group, and siloxy group; further preferred are halogen atom, hydroxyl, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, silyl group, and siloxy group; and most preferred are hydroxyl, acyloxy, and siloxy groups.

[0285] In addition, R 4a R 4b and R 4c The rings are optionally bonded together to form a ring. The preferred ring size is a 5-membered or 6-membered ring. Specific examples include cyclopentane rings, cyclohexane rings, etc.

[0286] [Chemical Formula 13]

[0287]

[0288] In formula (5),

[0289] Ar 5 Each of these independently represents a divalent aromatic group that optionally has substituents.

[0290] R 5a Each group is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aromatic group optionally having a substituent. Furthermore, in Ar... 5 In the case of substituents, the substituents and R 5a They can be optionally bonded together to form a ring.

[0291] e is an integer from 0 to 4, f is an integer from 0 to 5, and e + f > 0.

[0292] e is an integer from 0 to 4, f is an integer from 0 to 5, and e + f > 0. e is preferably 0 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 1. f is preferably 1 or more and 3 or less, as an upper limit, more preferably 2 or less, and most preferably 1.

[0293] (Ar) 5 )

[0294] Ar 5 Each of these independently represents a divalent aromatic group that optionally has substituents.

[0295] Ar 5 The preferred ring size is a 5-membered or 6-membered ring. Specific examples include benzene rings and thiophene rings.

[0296] As Ar 5 Specific examples of the selected aromatic groups preferably include: benzene rings, naphthyl rings, anthracene rings, furan rings, thiophene rings, benzofuran rings, benzothiophene rings, and structures formed by connecting 2 to 5 of these aromatic groups. More preferably, benzene rings and thiophene rings are also included, with thiophene rings being the most preferred. Furthermore, Ar... 5 The substituents therein are optionally associated with R 5a They bond together to form a ring. The preferred ring size is a 5-membered or 6-membered ring. Specific examples of rings include cyclopentane rings and cyclohexane rings.

[0297] As Ar 5 The selected aromatic group optionally has a substituent group selected from group G. 1Substituents in the compound. From the viewpoint of compound stability, more preferred substituents are hydroxyl, alkoxy, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl, halogen atom, silyl, and silanoxy, further preferred are halogen atom, hydroxyl, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl, silyl, and silanoxy, particularly preferred are hydroxyl, acyloxy, and silanoxy.

[0298] (R) 5a )

[0299] R 5a Each of the following groups is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aromatic group optionally having a substituent. R 5a The preferred solution and R in equation (4) 4c The scope is the same.

[0300] Furthermore, in Ar 5 In the case of substituents, the substituents and R 5a They can be optionally bonded together to form a ring.

[0301] [A] 11 ]

[0302] A 11 It is a group represented by formula (6) or formula (7) below.

[0303] From the perspective that stronger electron-withdrawing properties would increase the EO coefficient, A 11 Preferably, it has electron-withdrawing groups as substituents, more preferably it has two or more cyano groups as substituents, even more preferably it has two, three or four cyano groups as substituents, and particularly preferably it has two or three cyano groups as substituents.

[0304] [Chemical Formula 14]

[0305]

[0306] In formula (6),

[0307] * is the L in equation (1) 11 The bonding positions.

[0308] R 61 and R 62 Each of the groups independently is selected from the group consisting of alkyl groups optionally having substituents, aromatic groups optionally having substituents, halogen atoms, alkyl sulfonyl groups optionally having substituents, and aralkyl groups optionally having substituents.

[0309] X61 For O or S.

[0310] (R) 61 R 62 )

[0311] R 61 and R 62 Each of the groups independently is selected from the group consisting of alkyl groups optionally having substituents, aromatic groups optionally having substituents, halogen atoms, alkyl sulfonyl groups optionally having substituents, and aralkyl groups optionally having substituents.

[0312] As R 61 and R 62 Among the selected groups, the most preferred are alkyl groups that optionally have substituents and aromatic groups that optionally have substituents.

[0313] More preferred examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, cyclohexyl, and dodecyl. More preferably, methyl and ethyl groups are listed, with methyl being the most preferred.

[0314] More preferred examples of aromatic groups include: benzene ring, naphthalene ring, thiophene ring, and even more preferred examples include: benzene ring, thiophene ring, and most preferred example is benzene ring.

[0315] In R 61 and R 62 In the case of substituents, the substituents optionally present are preferably selected from the substituent group G. 1 From the viewpoint of compound stability, more preferred specific examples are acyloxy, acyl group, halogen atom, silyl group, and siloxy group, further preferred are halogen atom and siloxy group, and most preferred are hydroxyl group, acyloxy, and siloxy group.

[0316] [X] 61 ]

[0317] X 61 It can be O or S. From the viewpoint of improving the electro-optic effect, O is preferred.

[0318] [Chemical Formula 15]

[0319]

[0320] In formula (7),

[0321] * is the L in equation (1) 11 The bonding positions.

[0322] R 73The group is selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an aromatic group optionally having a substituent, an acyl group optionally having a substituent, an alkoxycarbonyl group optionally having a substituent, and an aralkyl group optionally having a substituent.

[0323] (R) 73 )

[0324] R 73 It is a group selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an aromatic group optionally having a substituent, an acyl group optionally having a substituent, an alkoxycarbonyl group optionally having a substituent, and an aralkyl group optionally having a substituent.

[0325] As R 73 The selected groups are more preferably hydrogen atoms, alkyl groups optionally having substituents, aromatic groups optionally having substituents, acyl groups optionally having substituents, alkoxycarbonyl groups optionally having substituents, and aralkyl groups optionally having substituents. More preferably, they are alkyl groups optionally having substituents, acyl groups optionally having substituents, alkoxycarbonyl groups optionally having substituents, and aralkyl groups optionally having substituents. From the viewpoint of compound stability, acyl groups optionally having substituents and aralkyl groups optionally having substituents are most preferred.

[0326] More preferred specific examples of acyl groups include benzoyl group and acetyl group, with benzoyl group being the most preferred example.

[0327] In R 73 In the case of substituents, the substituents optionally present are preferably selected from the substituent group G. 1 From the viewpoint of preventing the aggregation of compounds, more preferred specific examples are hydroxyl, alkoxy, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, halogen atom, silyl group, and siloxy group; further preferred are halogen atom, hydroxyl, dialkylamino, aromatic amino, aromatic alkylamino, acyloxy, acyl group, silyl group, and siloxy group; and most preferred are hydroxyl, acyloxy, and siloxy group.

[0328] (X) 61 )

[0329] X 61 It can be either O or S.

[0330] From the perspective of improving electron-withdrawing properties, X 61 O is preferred.

[0331] The compound represented by formula (1) in this embodiment is optionally bonded with the above-described dendritic compound. From the viewpoint of improving nonlinear optical activity, the compound represented by general formula A or general formula B is preferred as the dendritic compound.

[0332] In the compound shown in formula (1), the bonding position with the dendritic compound is not particularly limited. From the viewpoint of compound stability, Z is preferred. 12 Z 13 L 11 Or A 11 Z is preferred 12 or L 11 .

[0333] [Specific examples of compounds represented by formula (1)]

[0334] Specific examples of compounds represented by formula (1) in this embodiment are shown below. The present invention is not limited to these.

[0335] [Chemical Formula 16]

[0336]

[0337] [Chemical Formula 17]

[0338]

[0339] [Chemical Formula 18]

[0340]

[0341] [Chemical Formula 19]

[0342]

[0343] [Chemical Formula 20]

[0344]

[0345] [Chemical Formula 21]

[0346]

[0347] [Chemical Formula 22]

[0348]

[0349] [Chemical Formula 23]

[0350]

[0351] [Chemical Formula 24]

[0352]

[0353] [Chemical Formula 25]

[0354]

[0355] [Chemical Formula 26]

[0356]

[0357] [Chemical Formula 27]

[0358]

[0359] [Chemical Formula 28]

[0360]

[0361] [Chemical Formula 29]

[0362]

[0363] [Chemical Formula 30]

[0364]

[0365] [Chemical Formula 31]

[0366]

[0367] [Chemical Formula 32]

[0368]

[0369] [Chemical Formula 33]

[0370]

[0371] [Chemical Formula 34]

[0372]

[0373] [Chemical Formula 35]

[0374]

[0375] [Chemical Formula 36]

[0376]

[0377] [Chemical Formula 37]

[0378]

[0379] [Chemical Formula 38]

[0380]

[0381] [Chemical Formula 39]

[0382]

[0383] [Chemical Formula 40]

[0384]

[0385] [Chemical Formula 41]

[0386]

[0387] [Chemical Formula 42]

[0388]

[0389] [Chemical Formula 43]

[0390]

[0391] [Chemical Formula 44]

[0392]

[0393] [Chemical Formula 45]

[0394]

[0395] [Chemical Formula 46]

[0396]

[0397] [Chemical Formula 47]

[0398]

[0399] [Chemical Formula 48]

[0400]

[0401] [Chemical Formula 49]

[0402]

[0403] [Chemical Formula 50]

[0404]

[0405] [Chemical Formula 51]

[0406]

[0407] [Chemical Formula 52]

[0408]

[0409] [Chemical Formula 53]

[0410]

[0411] [Chemical Formula 54]

[0412]

[0413] [Chemical Formula 55]

[0414]

[0415] [Chemical Formula 56]

[0416]

[0417] [Chemical Formula 57]

[0418]

[0419] [Chemical Formula 58]

[0420]

[0421] [Chemical Formula 59]

[0422]

[0423] [Chemical Formula 60]

[0424]

[0425] [Chemical Formula 61]

[0426]

[0427] [Chemical Formula 62]

[0428]

[0429] [Chemical Formula 63]

[0430]

[0431] [Chemical Formula 64]

[0432]

[0433] [Chemical Formula 65]

[0434]

[0435] [Chemical Formula 66]

[0436]

[0437] [Chemical Formula 67]

[0438]

[0439] [Chemical Formula 68]

[0440]

[0441] [Chemical Formula 69]

[0442]

[0443] [Chemical Formula 70]

[0444]

[0445] [Chemical Formula 71]

[0446]

[0447] [Chemical Formula 72]

[0448]

[0449] [Chemical Formula 73]

[0450]

[0451] [Chemical Formula 74]

[0452]

[0453] [Chemical Formula 75]

[0454]

[0455] [Chemical Formula 76]

[0456]

[0457] [Chemical Formula 77]

[0458]

[0459] [Chemical Formula 78]

[0460]

[0461] [Chemical Formula 79]

[0462]

[0463] [Chemical Formula 80]

[0464]

[0465] [Chemical Formula 81]

[0466]

[0467] [Chemical Formula 82]

[0468]

[0469] [Chemical Formula 83]

[0470]

[0471] [Chemical Formula 84]

[0472]

[0473] [Chemical Formula 85]

[0474]

[0475] [Chemical Formula 86]

[0476]

[0477] [Chemical Formula 87]

[0478]

[0479] [Chemical Formula 88]

[0480]

[0481] [Chemical Formula 89]

[0482]

[0483] [Chemical Formula 90]

[0484]

[0485] [Chemical Formula 91]

[0486]

[0487] [Chemical Formula 92]

[0488]

[0489] [Chemical Formula 93]

[0490]

[0491] [Chemical Formula 94]

[0492]

[0493] [Chemical Formula 95]

[0494]

[0495] [Chemical Formula 96]

[0496]

[0497] [Chemical Formula 97]

[0498]

[0499] [Chemical Formula 98]

[0500]

[0501] [Chemical Formula 99]

[0502]

[0503] [Chemical Formula 100]

[0504]

[0505] [Chemical Formula 101]

[0506]

[0507] [Chemical Formula 102]

[0508]

[0509] [Chemical Formula 103]

[0510]

[0511] [Chemical Formula 104]

[0512]

[0513] [Chemical Formula 105]

[0514]

[0515] [Chemical Formula 106]

[0516]

[0517] [Chemical Formula 107]

[0518]

[0519] [Chemical Formula 108]

[0520]

[0521] [Chemical Formula 109]

[0522]

[0523] [Chemical Formula 110]

[0524]

[0525] [Chemical Formula 111]

[0526]

[0527] [Chemical Formula 112]

[0528]

[0529] [Chemical Formula 113]

[0530]

[0531] (In the formula, OTBS represents tert-butyldimethylsiloxy, and Ph represents phenyl.)

[0532] <Nonlinear Optically Active Polymers>

[0533] The nonlinear optically active polymer compound in this embodiment is formed by attaching a group (hereinafter also referred to as "the group derived from the compound shown in formula (1)") obtained by removing at least one hydrogen atom from the compound shown in formula (1) to a repeating unit in the polymer compound.

[0534] In the nonlinear optically active polymer compound of this embodiment, groups derived from the compound shown in formula (1) may be present as part of the main chain of the repeating unit in the polymer compound, or groups derived from the compound shown in formula (1) may be bonded as part of the side chain.

[0535] Furthermore, the aforementioned dendritic compounds are optionally bonded to groups derived from compounds represented by formula (1) above.

[0536] As a polymer, there is no particular limitation, but specific examples can be listed, including: poly(meth)acrylates (e.g., polymethyl methacrylate (PMMA), polydicyclopentyl methacrylate (poly DCPMA), polyadamantane methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), polymethyl methacrylate carbonylaminoethyl ester, etc.), polyamides, polyimides, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, polycarbonates, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyesters, polyolefins, polyphenylene sulfide, aromatic polyamines, polyamines, polyureas, silicone resins, epoxy resins, polyvinyl chloride, fluoropolymers, and copolymers thereof, etc. (Meth)acrylic acid refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to (meth)acrylates, etc.

[0537] In particular, from the viewpoint of being generally excellent as optical materials, the group consisting of poly(meth)acrylates, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymers, maleimide-olefin copolymers, maleimide-methyl methacrylate copolymers, polycarbonate, and copolymers thereof is more preferred. From the viewpoint of compound stability, polystyrene, polymethacrylates, maleimide-styrene copolymers, and maleimide-methyl methacrylate copolymers are most preferred. Preferred examples of polymethacrylates include: polyadamantane methacrylate (polyAdMA), polyalkyloxycarbonylaminoethyl methacrylate, polymethyl methacrylate (PMMA), and polymethacrylate (cyclic or linear) alkyl esters.

[0538] The bonding mode between the groups derived from the compound shown in formula (1) and the polymer compound is not particularly limited. For example, they can be bonded via (thio)carbamate bonds, (thio)urea bonds, (thio)amide bonds, carbon-carbon bonds, (thio)ester bonds, (thio)ether bonds, etc. (Thio)carbamate refers to at least one of the groups selected from carbamates and thiocarbamates, as do (thio)urea, (thio)ester, (thio)ether, and (thio)amide. In particular, from the viewpoint of compound stability, carbamate bonds, carbon-carbon bonds, ester bonds, and ether bonds are preferred, with carbamate bonds being the most preferred.

[0539] The number of bonds between each group derived from the compound shown in formula (1) and the polymer is preferably 1 to 3, more preferably 1 to 2. That is, as an option, the nonlinear optically active polymer can be formed by bonding a group obtained by removing preferably 1 to 3, more preferably 1 to 2 hydrogen atoms from the compound shown in formula (1) above with the polymer.

[0540] The hydrogen-containing sites removed from the groups derived from the compound shown in formula (1) are not particularly limited as long as they are groups containing hydrogen atoms, but preferably Z of formula (1). 11 Z 12 Z 13 and / or L 11 The hydrogen atoms it contains, more preferably Z 12 Z 11 or L 11 The most preferred number of hydrogen atoms is Z. 12 It contains hydrogen atoms.

[0541] The nonlinear optically active polymer compound in this embodiment optionally has a crosslinking group. By having a crosslinking group, it can be crosslinked after polarization treatment, thus improving the durability of the compound. Examples of crosslinking groups include: vinyl, acryloyl, methacryloyl, allyl, thiol, polyamine, polyol, isocyanate, cyanoacryloyl, cinnamyl, cinnamyl, cinnamylene, cinnamyleneacetyl, α-methylcinnamyl, α-methylcinnamyleneacetyl, α,γ-dimethylcinnamyl, α,γ-dimethylcinnamyleneacetyl, α-phenylcinnamyl, α-phenylcinnamyleneacetyl, α-phenoxycinnamyl, α-phenoxycinnamyleneacetyl, α-cyanocinnamyl, α-cyanocinnamyleneacetyl Acyl groups, chalcone residues, oxetyl groups, epoxy groups, isocoumarin residues, 2,5-dimethoxystilbene residues, thymine residues, styrylpyridinium residues, maleimide residues, α-phenylmaleimide residues, anthracene residues, 2-pyranone residues, vinyl ether groups, trifluorovinyl ether groups, benzocyclobutenyl groups, and their derivatives are preferred. Examples of preferred compounds include acryloyl groups, methacryl groups, thiol groups, isocyanate groups, capped isocyanate groups, cinnamyl groups, cinnamylene groups, α-cyanocinnamylene groups, anthracene residues, and maleimide residues. From the viewpoint of compound stability, isocyanate groups and capped isocyanate groups are preferred, with capped isocyanate groups being the most preferred.

[0542] [Specific examples of nonlinear optically active polymers]

[0543] The following are specific examples of repeating units that may be included in the nonlinear optically active polymer compounds of this embodiment. The invention is not limited to these examples.

[0544] [Chemical Formula 114]

[0545]

[0546] [Chemical Formula 115]

[0547]

[0548] [Chemical Formula 116]

[0549]

[0550] [Chemical Formula 117]

[0551]

[0552] [Chemical Formula 118]

[0553]

[0554] [Chemical Formula 119]

[0555]

[0556] [Chemical Formula 120]

[0557]

[0558] [Chemical Formula 121]

[0559]

[0560] [Chemical Formula 122]

[0561]

[0562] [Chemical Formula 123]

[0563]

[0564] [Chemical Formula 124]

[0565]

[0566] [Chemical Formula 125]

[0567]

[0568] [Chemical Formula 126]

[0569]

[0570] (In the formula, Ph represents phenyl, and s, n, m, o, p, r, s, t, u, v represent the molar percentage of repeating units in the nonlinear optically active polymer compound, which is greater than 0 and less than 1.)

[0571] The repeating units in nonlinear optically active polymers can be arranged in a voluntary, different order.

[0572] As described above, the repeating units of the nonlinear optically active polymers can optionally have different orders; that is, the nonlinear optically active polymers can be nonlinear optically active polymers that are block copolymers, or they can be nonlinear optically active polymers that are random copolymers.

[0573] Nonlinear Optical Materials

[0574] The nonlinear optical material in this embodiment is composed of at least one selected from the group consisting of nonlinear optically active compounds and nonlinear optically active polymers.

[0575] [Nonlinear optically active compounds]

[0576] As an alternative, the nonlinear optical material in this embodiment uses the aforementioned nonlinear optically active compound. The nonlinear optically active compound is the compound represented by formula (1) above. The definitions of each group in the nonlinear optically active compound and their preferred embodiments are as described with respect to formula (1).

[0577] Nonlinear optically active compounds can be dispersed in polymer materials described later for use.

[0578] [Nonlinear optically active polymers]

[0579] As an example, the nonlinear optical material in this embodiment uses the aforementioned nonlinear optically active polymer compound. The nonlinear optically active polymer compound is formed by bonding a group obtained by removing at least one hydrogen atom from the compound shown in formula (1) above with the polymer compound.

[0580] The definitions and preferred schemes of the various groups in nonlinear optically active polymers are as described above.

[0581] The percentage of groups derived from the compound represented by formula (1) in a nonlinear optically active polymer can be expressed as the ratio of the total mass of the nonlinear optically active polymer to the mass of the groups derived from the compound represented by formula (1), or as the molar percentage of the compound represented by formula (1) to the total number of repeating units of the nonlinear optically active polymer. When expressed as a mass ratio, there is no particular limitation on the percentage of groups derived from the compound represented by formula (1) in the nonlinear optically active polymer. From the viewpoint of balancing electro-optic effects and solubility, when the total mass of the nonlinear optically active polymer is set to 100, the lower limit of the mass of the groups derived from the compound represented by formula (1) is preferably 1 or more, more preferably 10 or more, and even more preferably 20 or more. The upper limit is preferably 80 or less, more preferably 60 or less, and even more preferably 50 or less.

[0582] When expressed as a molar percentage, there are no particular limitations. From the viewpoint of balancing electro-optic effects and solubility, the lower limit of the molar percentage of groups derived from the compound shown in formula (1) relative to the total of each repeating unit of the nonlinear optically active polymer 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 60 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less.

[0583] The content of groups derived from the compound shown in formula (1) in nonlinear optically active polymers is determined by... 1 Calculations using methods such as ¹H-NMR, absorbance measurement, and gel permeation chromatography (GPC) are preferred. 1 ¹H-NMR and absorbance measurements were used to calculate the optimal selection. 1 H-NMR calculations.

[0584] As passed 1 A specific method for calculating the content of groups derived from the compound shown in formula (1) in a nonlinear optically active polymer by H-NMR is as follows: The molar ratio of the compound shown in formula (1) to each repeating unit of the nonlinear optically active polymer is calculated by taking the spectral integral value of a specific hydrogen atom derived from the compound shown in formula (1) as a reference and comparing it with the spectral integral value of a specific hydrogen atom of a group possessed by each repeating unit of the nonlinear optically active polymer. Based on this molar ratio, the apparent mass ratio can be calculated, and the content of groups derived from the compound shown in formula (1) in the nonlinear optically active polymer can be determined.

[0585] As a specific method for calculating the content of groups derived from the compound shown in formula (1) in a nonlinear optically active polymer by absorbance measurement, the maximum absorbance obtained by dissolving the compound shown in formula (1) into a solution of a specified concentration and measuring the absorbance is divided by the concentration. The result is calculated based on the ratio of the value obtained by similarly measuring the absorbance of the nonlinear optically active polymer to the aforementioned value. The absorbance is measured using a UV-Vis-NIR spectrophotometer.

[0586] There is no particular limitation on the weight-average molecular weight of the nonlinear optically active polymer compound, but to improve durability, it is preferably 0.5 million or more, more preferably 10,000 or more, and even more preferably 30,000 or more.

[0587] Furthermore, for the sake of solubility, it is preferable to have a concentration of 500,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less.

[0588] The weight-average molecular weight of nonlinear optically active polymers was determined by GPC using polystyrene as a standard.

[0589] There are no particular restrictions on the molecular weight distribution of the nonlinear optically active polymer compound, but it is preferably 3 or less, more preferably 2.8 or less, and even more preferably 2.5 or less.

[0590] From the perspective of performance improvement, it is preferable that the molecular weight distribution of the nonlinear optically active polymer compound is below 3.

[0591] The molecular weight distribution of nonlinear optically active polymers was determined by measuring the ratio of number-average molecular weight to weight-average molecular weight using polystyrene as a standard by GPC.

[0592] There are no particular limitations on the glass transition temperature (Tg) of the nonlinear optically active polymer compound, which is typically 40°C to 400°C. To improve heat resistance, it is preferably 45°C or higher, more preferably 50°C or higher, and even more preferably 80°C or higher. Furthermore, from the viewpoint of polarization process, it is preferably 330°C or lower, more preferably 300°C or lower, even more preferably 280°C or lower, and particularly preferably 250°C or lower.

[0593] The Tg of nonlinear optically active polymers is confirmed by measuring the temperature at the intersection of the slope of the rising portion of the DSC curve accompanying the glass transition with the baseline using differential scanning calorimetry (DSC).

[0594] There is no particular limitation on the decomposition temperature (Td) of the nonlinear optically active polymer compound, but it is preferably above 0°C, more preferably above 40°C, and even more preferably above 50°C. Furthermore, it is preferably below 500°C, more preferably below 400°C, even more preferably below 350°C, and particularly preferably below 300°C.

[0595] The Td of nonlinear optically active polymers was confirmed by measuring the temperature at which a 5% mass reduction occurs using a thermogravimetric differential thermal analysis (TG-DTA) device.

[0596] [Applications of Nonlinear Optical Materials]

[0597] There are no particular limitations on the applications of nonlinear optical materials; for example, nonlinear optical elements and electric field sensors can be listed. Nonlinear optical elements are particularly preferred.

[0598] <Composition>

[0599] The composition in this embodiment is a mixture containing the aforementioned nonlinear optical material and a solvent. When at least one of the compounds shown in formula (1) is included as the nonlinear optical material, the composition may further contain a polymeric material. Furthermore, the composition may also contain compounds exhibiting nonlinear optical activity other than the aforementioned nonlinear optical materials.

[0600] The composition in this embodiment is, for example, a composition containing at least one of the compounds shown in formula (1) above, a polymer material and a solvent, or a composition containing at least one of the nonlinear optically active polymer compounds formed by bonding a group obtained by removing at least one hydrogen atom from the compound shown in formula (1) to a repeating unit in the polymer compound and a solvent, or a composition containing at least one of the compounds shown in formula (1) above, at least one of the nonlinear optically active polymer compounds and a solvent.

[0601] [Nonlinear Optical Materials]

[0602] The nonlinear optical material in the composition uses at least one selected from the group consisting of the aforementioned nonlinear optically active compounds and nonlinear optically active polymers. The definitions and preferred embodiments of the groups in the nonlinear optically active compounds and nonlinear optically active polymers are as described above.

[0603] [Solid content]

[0604] The amount of solids refers to the amount of components other than the solvent contained in the composition. It should be noted that even if a component other than the solvent is a liquid at room temperature, it is not contained in the solvent but is contained in the solids.

[0605] There is no particular limitation on the content of nonlinear optical material in the composition, but the more components exhibiting nonlinear optical activity, the better. For example, it is preferably 1 to 100 parts by mass relative to 100 parts by mass of solid components, more preferably 5 to 100 parts by mass, and even more preferably 10 to 100 parts by mass.

[0606] [Polymer Materials]

[0607] When the nonlinear optical material is a nonlinear optically active compound, it is preferable to use a polymeric material in the composition.

[0608] As a polymer material, there are no particular restrictions as long as it can disperse nonlinear optically active compounds. However, for use as an optical material, non-scattering transparent polymers are preferred. Examples include: (meth)acrylate polymers (e.g., polymethyl methacrylate (PMMA)), polyamides, polyimides, polycarbonates, polydicyclopentyl methacrylate (poly DCPMA), polyadamantane methacrylate (poly AdMA), poly(DCPMA-co-MMA), poly(AdMA-co-MMA), etc.), cyclic olefin polymers, cyclic olefin copolymers, polystyrene, polyethylene, polymethylpentene, polypropylene, polyvinyl alcohol (PVA), polyethylene terephthalate, polysulfone, polyethersulfone, polyester, polyolefins, polyphenylene sulfide, polyurea, silicone resins, epoxy resins, polyvinyl chloride, fluoropolymers, etc. From the viewpoint of molecular orientation, the group consisting of poly(meth)acrylate, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, polycarbonate, and copolymers thereof is preferred, and the group consisting of poly(meth)acrylate, polyvinyl chloride, polystyrene, polyimide, and polycarbonate is more preferred. Furthermore, as poly(meth)acrylate, poly(methyl methacrylate) is preferred.

[0609] The aforementioned organic polymers can be used alone or in combination.

[0610] There is no particular limitation on the content of polymeric material in the composition. From the viewpoint of coatability, it is preferably 0 to 99 parts by mass relative to 100 parts by mass of solid content, more preferably 0 to 95 parts by mass, and even more preferably 0 to 90 parts by mass.

[0611] [Solvent]

[0612] The solvent that can be used in the composition of this embodiment is not particularly limited as long as it is a solvent that can dissolve nonlinear optically active compounds and polymeric materials or nonlinear optically active polymeric compounds. Organic solvents are preferred, such as: aromatic hydrocarbons such as toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, and styrene; aliphatic hydrocarbons such as n-hexane and n-heptane; halogenated hydrocarbons such as chlorobenzene, o-dichlorobenzene, chloroform, dichloromethane, dibromomethane, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxytrifluorotoluene, and 3-methoxytrifluorotoluene; and acetone. Ketones such as ethyl methyl ketone, isopropyl methyl ketone, isobutyl methyl ketone, butyl methyl ketone, diacetone alcohol, diethyl ketone, cyclopentanone, and cyclohexanone; esters such as ethyl acetate, propyl acetate, phenyl acetate, 2-methoxyethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethyl lactate, γ-butyrolactone, ethyl benzoate, methyl benzoate, benzoyl benzoate, 2-ethylhexyl benzoate, and ethyl 4-methylbenzoate; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrole. Amides such as ketones; alcohols such as methanol, ethanol, propanol, 2-propanol, allyl alcohol, butanol, isobutanol, tert-butanol, pentanol, 2-methylbutanol, 2-methyl-2-butanol, cyclohexanol, 2-methylpentanol, octanol, 2-ethylhexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc.; diols such as ethylene glycol, propylene glycol, hexanediol, trimethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, etc.; diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether. Ethers such as 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, butanediol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc.; 1,3-dimethyl-2-imidazolinone; dimethyl sulfoxide, anisole, etc. These organic solvents can be used alone or in combination of two or more.

[0613] From the viewpoint of coatability, chlorobenzene, o-dichlorobenzene, 1,2-dichloroethane, trifluoromethylbenzene, 3-methoxytrifluorotoluene, 3-methoxytrifluorotoluene, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are more preferred, dibromomethane, cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are even more preferred, and cyclopentanone, cyclohexanone, toluene, anisole, and propylene glycol monomethyl ether acetate are particularly preferred.

[0614] There is no particular limitation on the solvent content in the composition. From the viewpoint of film uniformity, it is preferably 80 to 99 parts by mass relative to 100 parts by mass of the composition. From the viewpoint of ensuring the stability of the composition, it is more preferably 85 to 99 parts by mass, and even more preferably 85 to 98 parts by mass.

[0615] [Other ingredients]

[0616] In addition to nonlinear optical materials, polymer materials, and solvents, other components may be used in the composition.

[0617] Other components are not particularly limited as long as they do not impair the purpose of the composition and do not damage the effect of the present invention. They may contain antioxidants such as hydroquinone, ultraviolet absorbers such as benzophenone, rheology modifiers such as silicone oil and surfactants, adhesive aids such as silane coupling agents, crosslinking agents of polymer matrices, compatibilizers, curing agents, pigments, preservation stabilizers, defoamers, etc., as needed.

[0618] There are no particular restrictions on the other contents in the composition. From the viewpoint of film uniformity, the contents are preferably 0.001 to 10 parts by mass relative to 100 parts by mass of the composition, more preferably 0.01 to 5 parts by mass, and even more preferably 0.01 to 1 part by mass.

[0619] [Method for manufacturing the composition]

[0620] There are no particular limitations on the method of manufacturing the composition, as long as it includes the step of dissolving the above-mentioned nonlinear optical material in the above-mentioned solvent.

[0621] As one embodiment, a method for manufacturing the composition can be listed, comprising: a step of mixing the aforementioned polymeric material with the aforementioned solvent and heating and stirring to dissolve it; a step of mixing the solution with the aforementioned nonlinear optically active compound and stirring to dissolve it; and a step of filtering the solution using a filter. Furthermore, as another embodiment, a method for manufacturing the composition can be listed, comprising: a step of mixing the aforementioned nonlinear optically active polymeric compound with the aforementioned solvent and stirring to dissolve it; and a step of filtering the solution using a filter.

[0622] [Use of the composition]

[0623] There are no particular limitations on the use of the composition; it is typically used to form nonlinear optical materials into films or thin films.

[0624] Nonlinear optical materials formed into films or thin films can be used in nonlinear optical elements. That is, the composition can be used as an ink for forming nonlinear optical elements.

[0625] There are no particular limitations on the methods for producing films or thin films from the composition. For example, well-known methods such as injection molding, pressure molding, soft lithography, and wet coating can be listed. Among these, considering the simplicity of the manufacturing equipment, mass production, and film quality (uniformity of film thickness, fewer defects such as bubbles, etc.), wet coating methods such as spin coating, doctor blade coating, dip coating, and inkjet coating can be listed.

[0626] One approach is to coat a composition obtained by dissolving the aforementioned nonlinear optically active compound and the aforementioned polymeric material in the aforementioned solvent onto a substrate and then dry it. The drying process mentioned here refers to, for example, a process of drying by heating the substrate on a heating device such as a heating plate, or a process of drying the coated substrate by placing it in a chamber and applying a vacuum, or a combination of both. Furthermore, another approach is to coat a composition obtained by dissolving the aforementioned nonlinear optically active polymeric compound in the aforementioned solvent onto a substrate and then heat and vacuum dry it.

[0627] <Nonlinear Optical Elements>

[0628] The nonlinear optical element in this embodiment is made using the aforementioned nonlinear optical material. For example, the nonlinear optical element in this embodiment can be made using the aforementioned composition.

[0629] As a nonlinear optical element, there are no particular limitations as long as it uses the aforementioned nonlinear optical materials and operates based on nonlinear optical effects. Examples include wavelength conversion elements, photorefractive elements, and electro-optic elements. Among these, nonlinear optical elements operating based on electro-optic effects are preferred, and more specifically, electro-optic elements such as optical switches, optical modulators, and phase shifters are preferred. As one embodiment, an optical modulator incorporating the aforementioned nonlinear optical elements can be provided.

[0630] As an electro-optic element, it is preferably used as an element having a structure in which a film containing a nonlinear optical material is formed on a substrate and held by an electrode pair for inputting electrical signals.

[0631] Materials used to form such a substrate include, for example, metals such as aluminum, gold, iron, nickel, chromium, and titanium; semiconductors such as silicon, titanium dioxide, zinc oxide, and gallium-arsenic; glass; and plastics such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polysulfone, polyetherketone, and polyimide.

[0632] A conductive film can be formed on the surface of a substrate. Materials used for such a conductive film include, for example, 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-phenyleneacetylene), and polyacetylene. The conductive film is formed using known dry deposition methods such as evaporation and sputtering, and known wet deposition methods such as dip coating and electrolytic deposition, and can be patterned as needed. It should be noted that the conductive substrate or the conductive film formed on the substrate as described above is used as an electrode during polarization or as an electrode during the operation of the element (hereinafter also referred to as the "lower electrode" in this specification).

[0633] On the surface of the substrate, an adhesive layer for improving the adhesion between the film formed thereon and the substrate, a leveling layer for smoothing the unevenness of the substrate surface, or some kind of intermediate layer that provides these functions can also be formed as needed. There are no particular limitations on the materials used to form such a film; for example, known materials such as acrylic resins, methacrylic resins, amide resins, vinyl chloride resins, vinyl acetate resins, phenolic resins, polyurethane resins, vinyl alcohol resins, acetal resins, and copolymers thereof; crosslinks such as zirconium chelates, titanium chelates, silane coupling agents, and co-crosslinks thereof can be used.

[0634] The electro-optic element is preferably formed as an element containing a waveguide structure, and it is particularly preferred that the core layer of the waveguide contains the aforementioned nonlinear optical material.

[0635] A cladding layer (hereinafter referred to as the "lower cladding layer") may be formed between the core layer containing the aforementioned nonlinear optical material and the substrate. This lower cladding layer can be any cladding layer, as long as it has a lower refractive index than the core layer and is not penetrated during the formation of the core layer. Materials forming the lower cladding layer, for example, preferably include UV-curable or thermosetting resins such as acrylic, epoxy, oxetane, styrene, and silicone; polyimide; and glass.

[0636] After the core layer is formed from the aforementioned nonlinear optical material, a cladding layer (hereinafter referred to as the "upper cladding layer") can be further formed on top of it in the same manner as the lower cladding layer. Thus, a planar waveguide with the configuration of substrate / lower cladding layer / core layer / upper cladding layer is formed.

[0637] After the core layer is formed, it can be patterned using known semiconductor process technologies such as reactive ion etching (RIE), photolithography, and electron beam lithography to form a channel-type waveguide or a ridge-type waveguide. Alternatively, a portion of the core layer can be patterned and irradiated with UV light, an electron beam, or the like, causing a change in the refractive index of the irradiated portion to form a channel-type waveguide.

[0638] A basic electro-optic element can be formed by forming an electrode (hereinafter referred to as the "upper electrode") in a desired area of ​​the upper coating layer for applying an input electrical signal to the surface of the upper coating layer.

[0639] When a channel-type waveguide or a ridge-type waveguide is formed as described above, the pattern of the core layer can be configured into known device structures such as linear, Y-branch, directional coupler, and Mach-Zehnder types, and can be applied to known optical information communication devices such as optical switches, optical modulators, and phase shifters. As an example of its application in optical information communication devices, the application of an optical modulator having a nonlinear optical element that operates based on the aforementioned electro-optic effect can be cited.

[0640] Example

[0641] The following embodiments further illustrate the present invention. The present invention is not limited to the following embodiments; it can be implemented in any way without departing from its spirit.

[0642] [ 1 H-NMR and 13 [C-NMR determination]

[0643] Nuclear magnetic resonance spectroscopy (NMR spectroscopy) 1 H-NMR and 13 C-NMR was performed using a JNM-ECZ400S instrument manufactured by NEC Corporation, with CDCl3 as the solvent. The chemical shift δ of the tetramethylsilane from the internal standard is expressed in ppm. The symbols used have the following meanings.

[0644] s: singlet, d: doublet, dd: double doublet, t: triplet, m: multiplet, b: broad peak, J: coupling constant.

[0645] Compound EOD-001 was synthesized by the following method.

[0646] Synthesis of Compound 2

[0647] [Chemical Formula 127]

[0648]

[0649] In a 1L four-necked flask, under a nitrogen stream and at room temperature, compound 1 (25.3 g, 0.117 mol) was dissolved by stirring in N,N-dimethylformamide (superhydrated, 253 mL), followed by the addition of imidazole (15.9 g, 2.0 eq.). After cooling to an internal temperature of -6°C, tert-butyldimethylchlorosilane (TBDMSCl) (19.3 g, 1.1 eq.) was added in portions over 6 minutes at an internal temperature below 3°C, while stirring for 1.5 hours to restore the internal temperature to 26°C. The mixture was then cooled again to an internal temperature of -2°C and quenched with purified water (250 mL). Toluene (500 L) was added and stirred for a period of time, then allowed to stand and oil-water separation was performed. The aqueous layer was extracted with toluene (250 mL). The two toluene layers were combined and washed successively with saturated sodium bicarbonate aqueous solution (250 mL), purified water (250 mL), and saturated brine (100 mL), and then dried with sodium sulfate. The desiccant was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain crude product 2 (46.5 g), a pale yellow transparent liquid. The crude product was purified by silica gel column chromatography (Kanto Chemical Co., Ltd., silica gel 60N, spherical neutral, 63-210 μm, using 600 g, eluted with dichloromethane / hexane = 1 / 4) to obtain compound 2 (36.7 g, a colorless transparent liquid).

[0650] Synthesis of Compound 4

[0651] [Chemical Formula 128]

[0652]

[0653] In a 1L four-necked flask, under an argon atmosphere and at room temperature, compound 3 (20.0 g, 53.9 mmol), toluene (270 mL, ca. 0.2 M), and 2-ethylaniline (9.79 g, 1.5 eq.) were added. After argon bubbling for 20 minutes at room temperature, sodium tert-butoxide (12.9 g, 2.5 eq.) was added, followed by argon bubbling for another 10 minutes at room temperature. Simultaneously, palladium acetate (242 mg, 2 mol%) and (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (Binap) (1.34 g, 4 mol%) were added in a single batch. The mixture was heated and stirred at an internal temperature of 90–100 °C for 5 hours. After standing overnight at room temperature, the mixture was stirred at an internal temperature of 4 °C, and purified water (150 mL) was added for quenching. After stirring for a period of time, the mixture was allowed to stand and oil-water separation was performed. The aqueous layer was extracted with ethyl acetate (250 mL). After merging the two organic layers, the mixture was washed sequentially with purified water (200 mL) and saturated brine (100 mL), and dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a dark brown, oily crude product (36.9 g). This crude product was purified by silica gel column chromatography (Kanto Chemical Co., Ltd., silica gel 60N, spherical neutral, 63-210 μm, using 1.11 kg, eluted with ethyl acetate / hexane = 1 / 19) to give compound 4 (20.9 g, 90.3% yield, yellow, transparent, viscous substance).

[0654] Synthesis of Compound 5

[0655] [Chemical Formula 129]

[0656]

[0657] In a 500 mL four-necked flask, under an argon atmosphere and at room temperature, compound 4 (11.7 g, net weight 27.2 mmol), toluene (136 mL, ca. 0.2 M), and compound 2 (10.8 g, 1.2 eq.) were added. After argon bubbling for 20 minutes at room temperature, sodium tert-butoxide (6.53 g, 2.5 eq.) was added, followed by argon bubbling for another 14 minutes at room temperature. Simultaneously, tris(dibenzylacetone)dipalladium(0)(Pd2(dba)3) (498 mg, 2 mol%) and tri-tert-butylphosphonium tetrafluoroborate (631 mg, 8 mol%) were added in a single batch. The mixture was heated and stirred at an internal temperature of 90–100 °C for 6.5 hours.

[0658] After standing overnight at room temperature, the mixture was stirred at an internal temperature of 0°C and quenched with purified water (150 mL). After stirring for a period of time, the mixture was allowed to stand and oil-water separation was performed. The aqueous layer was extracted with ethyl acetate (200 mL). The two organic layers were combined and washed successively with purified water (100 mL) and saturated brine (100 mL), and dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a dark brown oily crude product (29.1 g). The crude product was purified by silica gel column chromatography (Kanto Chemical Co., Ltd., silica gel 60N, spherical neutral, 40-50 μm, using 720 g, eluted with ethyl acetate / hexane = 1 / 49 to 1 / 29) to obtain compound 5 (14.1 g, yield 78.5%, yellow transparent viscous substance).

[0659] Synthesis of Compound 6

[0660] [Chemical Formula 130]

[0661]

[0662] In a 500 mL four-necked flask under an argon atmosphere at room temperature, compound 5 (14.1 g, 21.3 mmol) was dissolved in tetrahydrofuran (superhydrated, 141 mL) with stirring. After cooling to an internal temperature of -74 °C, a 1.6 M n-butyllithium / n-hexane solution (14.6 mL, 1.1 eq.) was added dropwise over 8 minutes at an internal temperature below -65 °C. After stirring for 1 hour at an internal temperature between -68 °C and -74 °C, a THF solution of N,N-dimethylformamide (6.23 g, 4.0 eq.) (6.2 mL) was added dropwise over 4 minutes at an internal temperature below -66 °C. The mixture was stirred while being brought back to an internal temperature of 0 °C for 1 hour and 36 minutes, and then cooled again to an internal temperature of -24 °C. Quenching was performed with purified water (44 mL), followed by extraction twice with ethyl acetate (140 mL). The two organic layers were combined and washed successively with purified water (140 mL) and saturated brine (140 mL), then dried over anhydrous sodium sulfate. The desiccant was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain an orange viscous crude product (17.0 g). The crude product was purified by silica gel column chromatography (Kanto Chemical Co., Ltd., silica gel 60N, spherical neutral, 40-50 μm, 600 g, eluted with dichloromethane / hexane = 1 / 1 to 2 / 1) to obtain compound 6 (11.4 g, yield 76.7%, orange-red viscous oil).

[0663] Synthesis of compound EOD-001

[0664] [Chemical Formula 131]

[0665]

[0666] In a 200 mL three-necked flask, under a nitrogen stream and at room temperature, compound 6 (4.40 g, net weight 6.38 mmol), tetrahydrofuran (superhydrated, 11 mL), ethanol (superhydrated, 22 mL), and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malonitrile (3.61 g, 1.8 eq.) were added and stirred at room temperature for 20 hours. Then, the temperature was raised to 40 °C and stirred for 4 hours. The solution was concentrated under reduced pressure and purified by medium-pressure rapid column chromatography (Yamazen Corporation, using a general-purpose 2L column, eluting with ethyl acetate / hexane = 1 / 4 to 2 / 1) to give compound EOD-001 (3.82 g, yield 60.7%, dark green solid).

[0667] The following shows the NMR results for compound EOD-001.

[0668] 1 H-NMR (400MHz, CDCl3) δ7.77 (d,J=15.1Hz,1H), 7.52 (d,J=28.4Hz,6H), 7.33-7.08 (m,12H), 6.99-6.95 (m,3H), 6.81 (d,J=8.7Hz,2H), 6.60 ( d,J=15.6Hz,1H), 6.31(d,J=14.6Hz,2H), 4.95(s,2H), 4.03-4.01(m,2H), 3.98-3.95(m,2H), 2.36(q,J=7.5Hz,2H), 0.91(s,9H), 0.11(s,6H)

[0669] The compound EOD-002 was synthesized by the following method.

[0670] Synthesis of Compound 7

[0671] Compound 7 was synthesized using the same method as compound 10b described in Journal of Polymer Science Part A: Polymer Chemistry, 2010, 49, 47-54.

[0672] [Chemical Formula 132]

[0673]

[0674] Synthesis of compound EOD-002

[0675] [Chemical Formula 133]

[0676]

[0677] In a 500 mL three-necked flask, under a nitrogen stream and at room temperature, compound 7 (3.11 g, net weight 6.13 mmol), tetrahydrofuran (superhydrated, 100 mL), ethanol (superhydrated, 220 mL), and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malonitrile (2.86 g, eq. 1.486) were added and stirred at room temperature for 6 hours. Then, the temperature was raised to 35 °C and stirred for 4 hours. The solution was concentrated under reduced pressure and purified by medium-pressure rapid column chromatography (Yamazen Corporation, using a general-purpose 2L column, eluted with dichloromethane / hexane / ethyl acetate = 2 / 1 / 0.1) to give compound EOD-002 (2.59 g, yield 52.5%, dark green solid).

[0678] The following shows the NMR determination results for compound EOD-002.

[0679] 1 H-NMR (400MHz, CDCl3) δ7.79 (d, J=15.1Hz, 1H), 7.46 (m, 12H), 7.29 (t, J=4. 6Hz,1H), 7.15(d,J=15.6Hz,1H), 6.93(d,J=4.1Hz,1H), 6.56(d,J=15.1Hz,1 H), 6.34 (dd, J=9.1, 2.3Hz, 1H), 6.19 (d, J=2.3Hz, 1H), 5.18 (s, 2H), 3.73 (t ,J=5.7Hz,2H), 3.50(t,J=5.7Hz,2H), 3.04(s,3H), 0.87(s,9H), 0.07(s,6H)

[0680] The organic compound represented by structural formula (A) described in Japanese Patent No. 4453383 is used as compound EOD-003.

[0681] [Chemical Formula 134]

[0682]

[0683] The compound EOD-004 was synthesized by the following method.

[0684] Synthesis of Compound 8

[0685] [Chemical Formula 135]

[0686]

[0687] Under a nitrogen stream, 4-bromosalicylic acid aldehyde (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. The mixture was cooled to 0 °C in an ice bath, and then benzyl bromide (20.5 g, 0.12 mol) was added dropwise. The mixture was stirred at 0 °C for 2 hours. After the reaction, the mixture was heated to room temperature, and the reaction solution was injected 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 give compound 8 (7.60 g, 77.6% yield).

[0688] Synthesis of Compound 9

[0689] [Chemical Formula 136]

[0690]

[0691] Compound 8 (16.3 g, 56.1 mmol), diethyl-2-thienylmethylphosphonate (15.8 g, 67.3 mmol), and THF (163 mL) were mixed in a 500 mL three-necked flask under a nitrogen stream 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 injected 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 give compound 9 (17.4 g, 83.7% yield).

[0692] Synthesis of Compound 10

[0693] [Chemical Formula 137]

[0694]

[0695] Under a nitrogen stream, in a 500 mL three-necked flask, sodium tert-butoxide (11.0 g, 114.5 mmol), palladium acetate (103 mg, 0.46 mmol), and 2,2'-bis(diphenylphosphino-1-1')-binaphthyl (570 mg, 0.92 mmol) were added to a toluene (229 mL) solution of compound 9 (17.0 g, 45.8 mmol) and 2,4,6-trimethylaniline (9.30 g, 68.7 mmol). 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 give compound 10 (13.7 g, 70.3% yield).

[0696] Synthesis of Compound 11

[0697] [Chemical Formula 138]

[0698]

[0699] In a 1 L flask, 2-(N-methylaniline)ethanol (80.0 g, 0.53 mol) was mixed with pyridine (400 mL) and 1,4-dioxane (400 mL). After cooling to 0 °C, iodine (201 g, 0.80 mol) was 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 a saturated aqueous sodium thiosulfate solution. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 11 (74.0 g, yield 50.4%).

[0700] Synthesis of Compound 12

[0701] [Chemical Formula 139]

[0702]

[0703] Under a nitrogen stream, a DMF solution (200 mL) of compound 11 (20.0 g, 72.2 mmol) was cooled to 0 °C in a 500 mL flask, and tert-butyldimethylchlorosilane (11.90 g, 79.4 mmol) was added. The reaction solution was then heated to 25 °C and stirred for 2 hours. After the reaction, the reaction solution was injected 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 give compound 12 (22.9 g, 81.1% yield).

[0704] Synthesis of Compound 13

[0705] [Chemical Formula 140]

[0706]

[0707] Under a nitrogen stream, sodium tert-butoxide (6.72 g, 69.9 mmol), Pd2(dba)3 (512 mg, 0.56 mmol), and tri-tert-butylphosphine tetrafluoroborate (649 mg, 2.24 mmol) were added to a toluene (186 mL) solution of compound 10 (11.9 g, 28.0 mmol) and compound 12 (13.1 g, 33.6 mmol) in a 500 mL three-necked flask. The mixture was stirred at 100 °C for 6.5 h. 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 give compound 13 (12.1 g, 62.9% yield).

[0708] Synthesis of Compound 14

[0709] [Chemical Formula 141]

[0710]

[0711] Under a nitrogen stream, a THF (120 mL) solution of compound 13 (12.0 g, 17.4 mmol) was cooled to -78 °C in a 500 mL three-necked flask, and n-butyllithium (1.6 M n-hexane, 12 mL) was added. After stirring at -78 °C for 1 hour, DMF (5.4 mL) diluted with THF (5.0 mL) was added, and the mixture was heated to 0 °C and stirred for 3 hours. After the reaction, water (50 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 14 (9.09 g, 72.8% yield).

[0712] Synthesis of EOD-004

[0713] [Chemical Formula 142]

[0714]

[0715] In a 300 mL three-necked flask, under a nitrogen stream, ethanol (40 mL) was added to a tetrahydrofuran (20 mL) solution of compound 14 (0.50 g, 0.83 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malonitrile (0.34 g, 10.8 mmol), and the mixture was stirred at room temperature for 10 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to give EOD-004 (390 mg, yield 52.2%).

[0716] The following shows the NMR results for compound EOD-004.

[0717] 1 H-NMR (400MHz, CHLOROFORM-D) δ7.77 (d,J=15.1Hz, 1H), 7.57-7.48 (m,H), 7.35-7.33 (m, 3H), 7.28 (d, J=4.6Hz, 2H), 7.15 (d, J=16.0Hz, 1H), 6.95-6.89 (m, 5H), 6.59-6.56 ( m, 3H), 6.36-6.29 (m, 2H), 4.97 (s, 2H), 3.76 (t, J=6.2Hz, 2H), 3.44 (t, J=5.9Hz, 2H), 2 .96 (s, 3H), 2.34 (s, 3H), 1.95 (t, J=14.9Hz, 6H), 0.92-0.83 (m, 9H), 0.07-0.01 (m, 6H)

[0718] The compound EOD-005 was synthesized by the following method.

[0719] Synthesis of Compounds 1-2

[0720] [Chemical Formula 143]

[0721]

[0722] In a 1 L flask, a solution of 1.51 L of N,N-dimethylformamide in 151 g (1.00 mol) of 2-(N-methylaniline)ethanol was cooled to 0 °C, and then a solution of 560 mL of N,N-dimethylformamide in 187 g of N-bromosuccinimide (NBS) was added. The reaction solution was then stirred at room temperature for 7 hours. After the reaction was complete, the reaction solution was diluted with 800 mL of DCM and washed with a saturated aqueous solution of sodium thiosulfate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compounds 1-2 (214 g, 93.2% yield).

[0723] Synthesis of compounds 1-3

[0724] [Chemical Formula 144]

[0725]

[0726] Under a nitrogen stream, a DMF solution (253 mL) of compounds 1-2 (25.3 g, 11.7 mmol) and imidazole (15.9 g) was cooled to 0 °C in a 500 mL flask, and then tert-butyldimethylchlorosilane (19.3 g) was added. The reaction solution was then heated to 25 °C and stirred for 1.5 hours. After the reaction, the solution was injected 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 give compounds 1-3 (22.9 g).

[0727] Synthesis of compounds 1-4

[0728] [Chemical Formula 145]

[0729]

[0730] Under a nitrogen stream, sodium tert-butoxide (4.8 g), Pd2(dba)3 (45 mg), and tri-tert-butylphosphine tetrafluoroborate (250 mg) were added to a 100 mL toluene solution of compounds 1-3 (6.10 g, 20.0 mmol) and 2,4,6-trimethylaniline (6.9 g, 20.0 mmol). The mixture was stirred at 100 °C for 16 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compounds 1-4 (8.6 g).

[0731] Synthesis of compounds 1-5

[0732] [Chemical Formula 146]

[0733]

[0734] Under a nitrogen stream, in a 500 mL three-necked flask, a methanol (330 mL) solution of isophorone oxide (50.9 g, 0.330 mol) was cooled to -13 °C. 100 mL of 28% sodium methoxide and methanol solution was added, and the mixture was refluxed with stirring for 5 hours. After the reaction, water (200 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compounds 1-5 (41.2 g).

[0735] Synthesis of compounds 1-6

[0736] [Chemical Formula 147]

[0737]

[0738] Under a nitrogen stream, in a 500 mL three-necked flask, compound 8 (26.2 g) and 77.8 mL of 28% (w / w) sodium hydroxide aqueous solution were added to an ethanol (142 mL) solution of compounds 1-5 (41.2 g), and the mixture was heated under reflux for 5 hours with stirring. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain compounds 1-6 (52.90 g).

[0739] Synthesis of compounds 1-7

[0740] [Chemical Formula 148]

[0741]

[0742] Under a nitrogen stream, in a 500 mL three-necked flask, 6.23 g of sodium hydride (60% by mass in liquid paraffin) was added to a 120 mL solution of tetrahydrofuran containing compounds 1-6 (52.9 g). The mixture was cooled to -4 °C, and a 120 mL solution of tetrahydrofuran containing diethyl cyanomethylphosphonate (27.60 g) was slowly added dropwise while stirring. The mixture was then stirred at room temperature for 1 hour. After the reaction, 100 mL of water was added to the reaction solution, and the mixture was extracted with 100 mL of ethyl acetate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compounds 1-7 (39.7 g, 71% yield).

[0743] Synthesis of compounds 1-8

[0744] [Chemical Formula 149]

[0745]

[0746] Under a nitrogen stream, sodium tert-butoxide (16.56 g), Pd2(dba)3 (1.26 g), and tri-tert-butylphosphonium tetrafluoroborate (tert-Bu3PHBF4) (1.60 g) were added to a toluene (689 mL) solution of compounds 1-4 (32.0 g, 68.9 mmol) and 1-7 (27.67 g) in a 500 mL three-necked flask. The mixture was stirred at 100 °C for 5 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compounds 1-8 (42.7 g, 78.3% yield).

[0747] Synthesis of compounds 1-9

[0748] [Chemical Formula 150]

[0749]

[0750] Under a nitrogen stream, a toluene (137 mL) solution of compounds 1-8 (5.35 g, 6.84 mmol) was cooled to -76 °C in a 500 mL three-necked flask. A 1 M diisobutylaluminum hydride and n-hexane solution (8.5 mL) was slowly added dropwise, and the mixture was stirred at -68 to -62 °C for 4.5 hours. After the reaction, water (400 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (500 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compounds 1-9 (2.40 g, 44.8% yield).

[0751] Synthesis of EOD-005

[0752] [Chemical Formula 151]

[0753]

[0754] In a 300 mL three-necked flask, under a nitrogen stream, ethanol (40 mL) was added to a tetrahydrofuran (20 mL) solution of compounds 1-9 (2.20 g, 2.80 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malonitrile (1.15 g), and the mixture was stirred at room temperature for 10 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to give EOD-005 (1.30 g, yield 42.9%).

[0755] The following shows the NMR results for compound EOD-005.

[0756] 1 H-NMR (400MHz, CHLOROFORM-D) δ7.58-7.30 (m, 14H), 6.91 (t, 3H), 6.72 (d, J=4.6Hz, 1H), 6.55 (m, 2H), 6.29-6.41 (m, 3H), 4.91 (s, 2H) , 3.76 (t, J=6.2Hz, 2H), 3.49-3.41 (m, 5H), 2.44 (s, 2H), 2.31 (s, 3H), 1.95 (s, 6H), 1.51 (s, 2H), 0.92-0.83 (m, 6H), 0.07-0.01 (m, 6H)

[0757] The compound EOD-006 was synthesized by the following method.

[0758] Synthesis of compound 2-0

[0759] [Chemical Formula 152]

[0760]

[0761] Under a nitrogen stream, sodium tert-butoxide (4.8 g), Pd2(dba)3 (8.35 g), and tri-tert-butylphosphine tetrafluoroborate (10.59 g) were added to a toluene (2.28 L) solution of 1-benzyloxy-3-bromobenzene (120 g, 456 mmol) and 2,4,6-trimethylaniline (92.49 g) in a 500 mL three-necked flask. The mixture was stirred at 90 °C for 8 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 2-0 (77.33 g, yield 53.4%).

[0762] Synthesis of Compound 2-1

[0763] [Chemical Formula 153]

[0764]

[0765] Under a nitrogen stream, in a 500 mL three-necked flask, 14.6 g of sodium hydride (60% by mass in liquid paraffin) was added to a solution of compound 2-0 (77.0 g, 0.243 mol) in N,N-dimethylformamide (770 mL). The mixture was cooled to 0 °C, and a solution of (2-bromoethoxy)-tert-butyldimethylsilane (69.6 g) in DMF (70 mL) was slowly added dropwise while stirring. The mixture was then heated to 70 °C and stirred for 1.5 h, followed by stirring at 70 °C for 8 h. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 2-1 (24.4 g, 27.8% yield).

[0766] Synthesis of compound 2-2

[0767] [Chemical Formula 154]

[0768]

[0769] In a 500 mL three-necked flask, a solution of compound 2-1 (58.0 g, 0.122 mol) in N,N-dimethylformamide (580 mL) was cooled to 0 °C, and N-bromosuccinimide (21.7 g) was slowly added. The mixture was then cooled to 0 °C and stirred at room temperature for 3.5 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 2-2 (55.9 g, 81.0% yield).

[0770] Synthesis of Compounds 2-3

[0771] [Chemical Formula 155]

[0772]

[0773] In a 500 mL three-necked flask, a tetrahydrofuran (500 mL) solution of compound 2-2 (50.0 g, 90.2 mmol) was cooled to -74 °C, then cooled to -78 °C. A 1.6 M n-butyllithium hexane solution (62.0 mL) was slowly added dropwise, and the mixture was stirred for 30 min. Then, N,N-dimethylformamide (27.9 mL) was slowly added dropwise, and the mixture was stirred for 30 min, followed by stirring at room temperature for 3.5 h. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 2-3 (30.8 g, 65.1% yield).

[0774] Synthesis of compounds 2-4

[0775] [Chemical Formula 156]

[0776]

[0777] Under a nitrogen stream, a solution of isophorone oxide (19.2 g, 0.125 mol) in ethylene glycol (376 mL) was cooled to 0 °C in a 500 mL three-necked flask. 7.48 g of sodium hydride (60% by mass in liquid paraffin) was added, and the mixture was stirred at room temperature for 1 hour. After the reaction, 200 mL of cooling water was added to the reaction solution, and the mixture was extracted with n-hexane / ethyl acetate = 1 / 1 (v / v) (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compounds 2-4 (11.5 g, 46.6% yield).

[0778] Synthesis of compounds 2-5

[0779] [Chemical Formula 157]

[0780]

[0781] Under a nitrogen stream, in a 500 mL three-necked flask, compound 2-4 (12.1 g) and piperidine (54.8 mL) were added to an ethanol (142 mL) solution of compound 2-3 (27.9 g), and the mixture was refluxed at 78 °C for 16 hours with stirring. After the reaction, water (200 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (200 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 2-5 (27.8 g, yield 73.5%).

[0782] Synthesis of compounds 2-6

[0783] [Chemical Formula 158]

[0784]

[0785] Under a nitrogen stream, in a 500 mL three-necked flask, diethyl cyanomethylphosphonate (10.9 g) was added to a tetrahydrofuran (307 mL) solution of compound 2-5 (21.0 g, 30.70 mmol), and the mixture was cooled to -19 °C. Sodium tert-butoxide (5.90 g) was added while stirring, and the mixture was then stirred at 40 °C for 12 hours. After the reaction, water (300 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (300 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 2-6 (15.8 g, 72.0% yield).

[0786] Synthesis of compounds 2-7

[0787] [Chemical Formula 159]

[0788]

[0789] Under a nitrogen stream, a toluene (360 mL) solution of compound 2-6 (12.6 g, 17.8 mmol) was cooled to -75 °C in a 500 mL three-necked flask. A 1 M diisobutylaluminum hydride and n-hexane solution (40.0 mL) was slowly added dropwise, and the mixture was stirred at -75 °C for 2 hours, followed by stirring at -40 °C for 1 hour. The solution was then cooled to -75 °C, and a 1 M diisobutylaluminum hydride and n-hexane solution (19.6 mL) was slowly added dropwise, followed by stirring at -40 °C for 2 hours. After the reaction, ethyl acetate (200 mL) was added to the reaction solution, and the mixture was washed with water (400 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 2-7 (8.09 g, yield 58.4%).

[0790] Synthesis of EOD-006

[0791] [Chemical Formula 160]

[0792]

[0793] Under a nitrogen atmosphere, ethanol (20 mL) was added to a tetrahydrofuran (10 mL) solution of compound 2-7 (1.15 g, 0.70 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malonitrile (0.24 g) in a 300 mL three-necked flask, and the mixture was stirred at room temperature for 10 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain EOD-006 (700 mg, 98.7% yield).

[0794] The following shows the NMR results for compound EOD-006.

[0795] 1 H-NMR (400MHz, CHLOROFORM-D) δ7.85-8.14 (s, 1H), 7.27-7.65 (m, 14H), 6.82-7.00 (m, 3H), 6.62-6.80 (m, 1H) , 6.24-6.49 (m, 1H), 3.36-4.08 (m, 8H), 2.17-2.65 (m, 7H), 1.75-2.17 (m, 9H), 0.73-1.15 (m, 14H), 0.22 (s, 6H)

[0796] The compound EOD-007 was synthesized by the following method.

[0797] [Chemical Formula 161]

[0798]

[0799] In a 200 mL three-necked flask, a 45 mL solution of EOD-006 (0.70 g, 0.986 mmol) in tetrahydrofuran was chilled, and 9.86 mL of 1 M hydrochloric acid was slowly added while the mixture was chilled. The mixture was stirred at room temperature for 4 hours. After the reaction was complete, 50 mL of saturated brine was added to the reaction solution, and the mixture was extracted with 50 mL of ethyl acetate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to obtain EOD-007 (0.42 g, 86.7% yield).

[0800] The following shows the NMR results for compound EOD-007.

[0801] 1H-NMR (400MHz, CHLOROFORM-D) δ7.97 (s, 1H), 7.67-7.25 (m, 15H), 6.93 (s, 2H), 6.74 (d, J = 12.3Hz, 1H), 6.37 (d, J = 14.2H) z, 1H), 5.08 (d, J=57.2Hz, 2H), 3.87-3.67 (m, 8H), 2.45-2.17 (m, 7H), 2.06-1.79 (m, 9H), 1.55 (s, 1H), 1.09-0.84 (m, 6H)

[0802] The compound EOD-008 was synthesized by the following method.

[0803] Compound 5-1 was synthesized using the same method as compound RH described in MATERIALS CHEMISTRY FRONTIERS, 2018, 2, 901-909.

[0804] [Chemical Formula 162]

[0805]

[0806] Synthesis of Compound 5-2

[0807] [Chemical Formula 163]

[0808]

[0809] In a 200 mL three-necked flask under a nitrogen stream, a chloroform (35 mL) solution of compounds 2-7 (0.88 g, 1.25 mmol), 5-1 (0.661 g, 1.50 mmol), and 4-dimethylaminopyridine (DMAP) (15.2 mg) was slowly added to 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI·HCl) (6.21 g) while the mixture was still cold. The mixture was stirred at 65 °C for 4 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to give compound 5-2 (0.48 g, yield 34.0%).

[0810] Synthesis of EOD-008

[0811] [Chemical Formula 164]

[0812]

[0813] Under a nitrogen stream, in a 200 mL three-necked flask, ethanol (2 mL) was added to a tetrahydrofuran (2 mL) solution of compound 5-2 (215 mg, 0.19 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malonitrile (0.066 g), and the mixture was stirred at room temperature for 12 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to give EOD-008 (180 mg, yield 66.3%).

[0814] The following shows the NMR results for compound EOD-008.

[0815] 1 H-NMR (400MHz, CHLOROFORM-D) δ7.84 (s, 1H), 7.53-7.25 (m, 21H), 7.00-6.97 (m, 4H), 6.90 (s, 2H), 6.68 (d, J=12.8Hz, 2H), 6.26 (d, J=14 .2Hz,1H), 4.91(s,6H), 4.52(s,2H), 3.98(s,2H), 3.70(s,2H), 3.56(s,2H), 2.38(d,J=48.9Hz,6H), 0.96(d,J=28.4Hz,5H), 0.84(s,9H)

[0816] The compound EOD-009 was synthesized by the following method.

[0817] Synthesis of compound 3-1

[0818] [Chemical Formula 165]

[0819]

[0820] In a three-necked flask, 179.4 g of 2-(methylamino)ethanol was dissolved in 3.0 L of dichloromethane, and 271.0 g of imidazole was added. The mixture was cooled to -9 °C. While stirring at -9 °C, 300.0 g of tert-butyldimethylchlorosilane was slowly added, and the mixture was stirred for 15 hours within the range of -9 °C to 5 °C. After adding 3 L of water, the organic layer was separated and concentrated under reduced pressure to obtain compound 3-1 (350.8 g).

[0821] Synthesis of compound 3-2

[0822] [Chemical Formula 166]

[0823]

[0824] In a three-necked flask, under an argon flow, compound 3-1 (64.77 g) and B2307 (75.00 g) were dissolved in toluene (750 mL), and sodium tert-butoxide (60.26 g) was added. The mixture was heated to 60 °C to prepare solution A. In another container, under an argon flow, tris(dibenzylacetone)dipalladium (2.61 g) and (4-dimethylaminophenyl)di-tert-butylphosphine (Amphos) (3.03 g) were dissolved in toluene (75 mL). After stirring at 60 °C for 25 minutes, the solution was slowly added dropwise to solution A, and the mixture was stirred at 100 °C for 5 hours and 30 minutes. The reaction solution was then purified by silica gel column chromatography to give compound 3-2 (87.61 g).

[0825] Synthesis of compound 3-3

[0826] [Chemical Formula 167]

[0827]

[0828] In a three-necked flask, compound 3-2 (87.55 g) was dissolved in N,N-dimethylformamide (876 mL). After cooling to -10 °C, N-bromosuccinimide (271.0 g) was slowly added while stirring. The mixture was stirred at 0 °C to 10 °C for 3 hours. The reaction solution was then purified by silica gel column chromatography to give compound 3-3 (95.69 g).

[0829] Synthesis of compounds 3-4

[0830] [Chemical Formula 168]

[0831]

[0832] In a three-necked flask, under a nitrogen stream, compound 3-3 (90.00 g) was dissolved in THF (900 mL). After cooling to -74 °C, a 1.6 M n-butyllithium hexane solution (137.4 mL) was slowly added while stirring, and the mixture was stirred at -78 °C for 30 minutes. Then, a mixture of DMF (62 mL) and THF (60 mL) was slowly added dropwise to the reaction solution. 500 mL of water was added to the reaction solution, and after separating the organic layer, it was washed with saturated brine (300 mL) and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 3-4 (60.03 g).

[0833] Synthesis of compounds 3-5

[0834] [Chemical Formula 169]

[0835]

[0836] Under a nitrogen stream, in a 100 mL three-necked flask, compound 2-4 (5.12 g) and piperidine (8.50 mL) were added to an ethanol (20 mL) solution of compound 3-4 (8.60 g), and the mixture was refluxed at 78 °C for 6 hours with stirring. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with dichloromethane (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 3-5 (6.87 g, yield 44.5%).

[0837] Synthesis of compounds 3-6

[0838] [Chemical Formula 170]

[0839]

[0840] Under a nitrogen stream, in a 200 mL three-necked flask, diethyl cyanomethylphosphonate (3.8 g) was added to a tetrahydrofuran (83 mL) solution of compound 3-5 (8.3 g), and the mixture was cooled to -75 °C. A 1.6 M n-butyllithium hexane solution (10.1 mL) was slowly added while stirring, and the mixture was then stirred at 40 °C for 2 hours. After the reaction, water (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 3-6 (15.0 g, yield 57.9%).

[0841] Synthesis of compounds 3-7

[0842] [Chemical Formula 171]

[0843]

[0844] Under a nitrogen stream, a toluene (89 mL) solution of compound 3-6 (4.55 g, 7.55 mmol) was cooled to -78 °C in a 500 mL three-necked flask. A 1 M diisobutylaluminum hydride and n-hexane solution (9.43 mL) was slowly added dropwise, and the mixture was stirred at -78 °C for 2 hours, followed by stirring at -40 °C for 1 hour. After the reaction, ethyl acetate (100 mL) was added to the reaction solution, and the mixture was washed with water (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 3-7 (3.20 g, 70.0% yield).

[0845] Synthesis of compounds 3-8

[0846] [Chemical Formula 172]

[0847]

[0848] In a 200 mL three-necked flask, a 45 mL solution of tetrahydrofuran containing compound 3-7 (0.70 g, 0.986 mmol) was chilled, and 9.86 mL of 1 M hydrochloric acid was slowly added while the mixture was chilled. The mixture was stirred at room temperature for 4 hours. After the reaction was complete, 50 mL of saturated brine was added to the reaction solution, and the mixture was extracted with 50 mL of ethyl acetate. The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 3-8 (0.42 g, 86.7% yield).

[0849] Synthesis of EOD-009

[0850] [Chemical Formula 173]

[0851]

[0852] In a 300 mL three-necked flask under a nitrogen stream, ethanol (5 mL) was added to a tetrahydrofuran (2 mL) solution of compound 3-8 (0.70 g, 0.9 mmol) and 2-[3-cyano-4-methyl-5-phenyl-5-(trifluoromethyl)furan-2(5H)-ylidene]malonitrile (0.264 g), and the mixture was stirred at room temperature for 10 hours. After the reaction was complete, the solution was concentrated under reduced pressure and purified by silica gel chromatography to give EOD-009 (230 mg, yield 34.1%).

[0853] The following shows the NMR determination results for compound EOD-009.

[0854] 1 H-NMR (400MHz, CHLOROFORM-D) δ7.92 (d,J=16.5Hz,1H), 7.57-7.30 (m,13H), 6.71 (d,J=18.3Hz,1H), 6.40-6.32 (m,2H), 5.29 ( s,3H), 5.21-5.13 (m,2H), 3.92-3.85 (m,2H), 3.82-3.74 (m,4H), 3.51-3.48 (m,2H), 2.44 (t,J=10.3Hz,2H), 1.03-0.80 (m,10H)

[0855] Compound EOP-001 was synthesized by the following method.

[0856] Synthesis of compound 4-1

[0857] [Chemical Formula 174]

[0858]

[0859] In a 300 mL three-necked flask, a solution of tetrahydrofuran (100 mL) containing EOD-001 (2.50 g, 3.62 mmol) was chilled, and 1 M hydrochloric acid (36.2 mL) was slowly added while the mixture was chilled. The mixture was stirred at room temperature for 4 hours. After the reaction was complete, saturated brine (100 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was dried over sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel chromatography to give compound 4-1 (2.0 g, 95.6% yield).

[0860] Synthesis of Basic Polymer 1

[0861] [Chemical Formula 175]

[0862]

[0863] Methyl methacrylate (MMA) (12.8 g, 127.8 mmol), 1-adamantane methacrylate (28.2 g, 128.0 mmol), and ethyl 2-[(3,5-dimethylpyrazolyl)carbonylamino]methacrylate (16.1 g, 64.1 mmol) were dissolved in deoxytoluene (110 mL), followed by the addition of 2,2'-azobis(2,4-dimethylpentanonitrile) (V-65) (171 mg, 0.69 mmol). The reaction solution was then heated to 60 °C and stirred for 6 hours, followed by heating to 70 °C and stirring for another 2 hours. After the reaction, the reaction solution was cooled to 0 °C and added dropwise to hexane (120 mL). The resulting solid was filtered off. The filtered solid was washed with hexane (120 mL) and dried under vacuum to obtain base polymer 1 (35.0 g, 61% yield).

[0864] For the obtained base polymer 1, the molecular weight was determined by GPC using a GPC system (liquid delivery system; LC-20AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultipore HZ-M (4.6mm ID × 150mm L, 4μm, S) × 2, TSKguardcolumn SuperMP (HZ)-M, eluent: THF, column temperature: 40℃). The results showed that the weight-average molecular weight Mw was 114,000 and the number-average molecular weight Mn was 34,000.

[0865] Synthesis of basic polymer 2

[0866] [Chemical Formula 176]

[0867]

[0868] Styrene (3.00 g, 25.4 mmol) and N-ethylmaleimide (3.18 g, 25.4 mmol) were dissolved in dehydrated DMF (78 mL), and then 2,2'-azobis(2,4-dimethylpentanonitrile) (V-65) (67 mg, 0.20 mmol) was added. The reaction solution was then heated to 60 °C and stirred for 6 hours, followed by heating to 70 °C and stirring for another 2 hours. After the reaction, the reaction solution was cooled to 0 °C and added dropwise to hexane (120 mL), and the resulting solid was collected by filtration. The filtered solid was washed with hexane (120 mL) and dried under vacuum to obtain basic polymer 2 (3.2 g, 52% yield).

[0869] For the obtained base polymer 2, the molecular weight was determined by GPC using a GPC system (liquid delivery system; LC-20 AD, detector: RID) manufactured by Shimadzu Corporation (column: TSKgel SuperMultipore HZ-M (4.6mm ID × 150mm L, 4μm, S) × 2, TSKguardcolumn SuperMP (HZ)-M, eluent: THF, column temperature: 40℃). Two peaks were observed. The first was a weight-average molecular weight Mw of 114,000 and a number-average molecular weight Mn of 34,000. The second was a weight-average molecular weight Mw of 501,000.

[0870] Synthesis of EOP-001

[0871] [Chemical Formula 177]

[0872]

[0873] Under a nitrogen atmosphere, base polymer 1 (0.573 g) and compound 4-1 (300 mg) were dissolved in dehydrated 1,4-dioxane (32.7 mL), and dibutyltin dilaurate (DBTDL) (8 μ L) was added. The mixture was stirred in an oil bath at 110 °C for 3 hours. Then, dehydrated methanol (0.17 mL) was added, and the mixture was stirred in an oil bath at 110 °C for 2 hours. After cooling to room temperature, the reaction solution was added dropwise to hexane (150 mL), and the resulting solid was filtered off. The filtered solid was purified by treatment with activated clay (solvent: DCM), reprecipitation (good solvent: DCM, poor solvent: methanol), and vacuum drying at 60 °C to obtain EOP-001 (0.42 g).

[0874] The percentage of the group obtained by removing one hydrogen atom from compound 4-1 in EOP-001 was determined by the ratio of the mass absorptivity in the absorbance measurement using a spectrophotometer. The result showed that the percentage of the group obtained by removing one hydrogen atom from compound 4-1 was 38% by mass.

[0875] Compound EOP-002 was synthesized by the following method.

[0876] [Chemical Formula 178]

[0877]

[0878] Under a nitrogen atmosphere, base polymer 1 (0.141 g) and compound 4-1 (100 mg) were dissolved in dehydrated 1,4-dioxane (6.0 mL), and dibutyltin dilaurate (DBTDL) (7 μL) was added. The mixture was stirred in an oil bath at 110 °C for 3 hours. Then, dehydrated methanol (0.11 mL) was added, and the mixture was stirred in an oil bath at 110 °C for 2 hours. After cooling to room temperature, the reaction solution was added dropwise to hexane (50 mL), and the resulting solid was filtered off. The filtered solid was purified by treatment with activated clay (solvent: DCM), reprecipitation (good solvent: DCM, poor solvent: methanol), and vacuum drying at 60 °C to obtain EOP-002 (0.42 g).

[0879] The percentage of the group obtained by removing one hydrogen atom from compound 4-1 in EOP-002 was determined by the ratio of the mass absorptivity in the absorbance measurement using a spectrophotometer. The result showed that the percentage of the group obtained by removing one hydrogen atom from compound 4-1 was 47% by mass.

[0880] The following apparatus will be used in the following evaluation.

[0881] ・Spin coater: MS-A150 manufactured by MIKASA Co., Ltd.

[0882] • Heating plate: HP-1SA manufactured by AS ONE Co., Ltd.

[0883] • Oven: STH-120 small high-temperature chamber manufactured by ESPEC Corporation.

[0884] • Film thickness measurement: VertScan optical interferometer manufactured by Hitachi High Technology Co., Ltd.

[0885] ・Gold evaporation: EX-400-C08 manufactured by ULVAC Co., Ltd.

[0886] • Vacuum constant temperature dryer: Yamato Scientific Co., Ltd. DP-23.

[0887] • Temperature controller: Model 3060, manufactured by Lake Shore Cryotronics.

[0888] • Voltage application device: KEITHLEY 2470 SourceMeter.

[0889] • Laser light source: TSL-570 manufactured by Santec Corporation.

[0890] • Function generator: Teledyne Lexoy T3AFG10.

[0891] • Lock-in amplifier: LI5600 digital lock-in amplifier manufactured by NF Circuit Design Co., Ltd.

[0892] [Evaluation of Example 1]

[0893] (Cleaning of ITO substrate)

[0894] An ITO substrate for coating an intermediate layer composition was obtained by cleaning an ultrasonic cleaner in ultrapure water with a thin-film ITO substrate manufactured by EHC Corporation (which has an ITO film with a thickness of 9 nm on one side of a glass plate with a thickness of 0.7 mm; sheet resistance of the ITO film side surface: 519~578Ω / □).

[0895] Here, the glass plate contained in the ITO substrate is equivalent to the carrier, and the ITO film is equivalent to the electrode.

[0896] (Fabrication of a substrate with an intermediate layer film)

[0897] The compound shown in the following structural formula (hereinafter also referred to as "Material 1") was dissolved in cyclohexanone at a concentration of 3% by mass, and filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm to obtain intermediate layer composition A. Intermediate layer composition A was coated onto the side of an ITO substrate with an ITO film using a spin coater.

[0898] [Chemical Formula 179]

[0899]

[0900] An ITO substrate coated with interlayer composition A was pre-baked on a hot plate at 60°C for 1 minute, and then heat-treated in an oven at 230°C for 30 minutes to cure interlayer composition A, resulting in a substrate with an interlayer film formed on the ITO substrate. The film thickness of the obtained film was measured, and the result was 0.17 μm.

[0901] [Example 1]

[0902] (Making of Membrane 1)

[0903] A mixture of compound EOD-001 and polymer PMMA was dissolved in cyclohexanone at a mass ratio of 30:70, resulting in a total solids concentration of 13% by mass. The mixture was filtered through a PTFE (polytetrafluoroethylene) filter with a pore size of 0.22 μm to obtain composition 1. Composition 1 was then coated onto the side of a substrate with an interlayer film using a spin coater.

[0904] The substrate with the interlayer film coated with the above composition 1 was pre-baked on a heating plate at 60°C for 1 minute, and then subjected to heat drying treatment at 85°C for 15 hours in a vacuum constant temperature dryer to remove the solvent, thereby obtaining a substrate (substrate 1) with a film containing 30% by mass of nonlinear optical material formed on the substrate with the interlayer film. The film thickness of film 1 was measured, and the result was 1.36 μm.

[0905] The resulting film 1 has a sufficient thickness to exhibit electro-optic effects in devices such as optical modulators and optical switches.

[0906] (The fabrication of membrane 2)

[0907] The mixing ratio of EOD-001 to the polymer material PMMA was set to 40:60 (mass ratio). Otherwise, a substrate (substrate 2) containing a film containing nonlinear optical material was obtained in the same manner as film 1. The thickness of the obtained film (film 2) was measured, and the result was 1.24 μm.

[0908] (The fabrication of membrane 3)

[0909] The mixing ratio of EOD-001 and the polymer material PMMA was set to 50:50 (mass ratio). Otherwise, a substrate (substrate 3) containing a film containing nonlinear optical material was obtained in the same manner as the fabrication of film 1. The thickness of the obtained film (film 3) was measured, and the result was 1.11 μm.

[0910] (Fabrication of substrate with electrodes)

[0911] To achieve a film thickness of 50nm and an area of ​​30mm 2 Gold electrodes are formed by depositing gold onto the film surfaces of the substrates 1-3, each containing a nonlinear optical material, in a circular manner, thereby obtaining electrode-bearing substrates 1-3. The electrode-bearing substrates 1-3 have the following layer configuration for evaluating electro-optic effects.

[0912] Layer composition: ITO substrate (glass substrate + ITO film) / intermediate layer film / film containing nonlinear optical materials / gold electrode

[0913] [Polarization treatment]

[0914] The electrode substrates 1-3 are heated to 116°C using a temperature controller, and a voltage of 100V / μm is applied using a voltage application device. Simultaneously, they are cooled to room temperature with liquid nitrogen, thereby obtaining substrates 1-3 with polarization completed by aligning the nonlinear optical material in the electrode substrates 1-3 with the electric field.

[0915] [Electro-optic effect measurement]

[0916] For the polarized substrates 1 to 3, the electro-optic coefficients at a wavelength of 1.31 μm were measured using the same method as disclosed in CCTeng et al., Appl. Phys. Lett., 56, p1734 (1990) and Y. Shuto et al., J. Appl. Phys., 77, p4632 (1995).

[0917] Based on the measurement results, the increase in the electro-optic coefficient of substrate 2 relative to that of substrate 1 ("increase in electro-optic coefficient from 30% to 40% by mass") [times], and the increase in the electro-optic coefficient of substrate 3 relative to that of substrate 2 ("increase in electro-optic coefficient from 40% to 50% by mass") [times] were calculated. The results are shown in Table 1.

[0918] (Increase in electro-optic coefficient from 30% to 40% by mass)

[0919] = Electro-optic coefficient of substrate 2 / Electro-optic coefficient of substrate 1

[0920] (Increase in electro-optic coefficient from 40% to 50% by mass)

[0921] = Electro-optic coefficient of substrate 3 / Electro-optic coefficient of substrate 2

[0922] [Example 2]

[0923] Compound EOD-004 was used instead of compound EOD-001, and the substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 1. The results are shown in Table 1.

[0924] [Example 7]

[0925] Polymer 2 was used instead of PMMA, and an ITO substrate was used instead of the substrate with the interlayer film. Polarization was performed at 50V / μm. Otherwise, the substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 2. The results are shown in Table 1.

[0926] [Comparative Example 1]

[0927] Compound EOD-002 was used instead of compound EOD-001, and the substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 1. The results are shown in Table 1.

[0928] [Comparative Example 2]

[0929] Compound EOD-003 was used instead of compound EOD-001, and the substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 1. The results are shown in Table 1.

[0930] [Table 1]

[0931]

[0932] As can be clearly seen from Table 1, in Examples 1, 2 and 7, even if the concentration of the nonlinear optical material increases, the increase in the electro-optic coefficient is greater than 1. Even if the nonlinear optical material is at a high concentration, the electro-optic coefficient continues to increase.

[0933] On the other hand, it can be seen that in Comparative Example 1 and Comparative Example 2, the electro-optic coefficient increases from 40% to 50% by mass to 1.0, and the electro-optic coefficient no longer increases when the nonlinear optical material is at a high concentration.

[0934] [Example 3]

[0935] Compositions using EOP-001 instead of the mixture of compound EOD-001 and polymer material PMMA, and compositions using EOP-002 instead of the mixture of compound EOD-001 and polymer material PMMA, were obtained by the same method as in Example 1.

[0936] Using the obtained composition, substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 1. The results are shown in Table 2.

[0937] [Table 2]

[0938]

[0939] As can be clearly seen from Table 2, even if the concentration of the group obtained by removing one hydrogen atom from the compound shown in formula (1), i.e., the nonlinear optically active compound, increases from 38% by mass to 47% by mass, the electro-optic coefficient increases by more than 1. Even if the group obtained by removing one hydrogen atom from the nonlinear optically active compound is of high concentration, the electro-optic coefficient continues to increase.

[0940] On the other hand, Non-Patent Document 1 shows that if the concentration of the group obtained by removing one hydrogen atom from the compound exhibiting nonlinear optical activity increases from 36% by mass to 42% by mass, the increase in the electro-optic coefficient is significantly less than 1.0. When the concentration of the group obtained by removing one hydrogen atom from the compound exhibiting nonlinear optical activity is high, the electro-optic coefficient no longer increases.

[0941] [Example 4]

[0942] Using compound EOD-005 instead of compound EOD-001, compositions with a mixing ratio of EOD-005 to the polymer material PMMA of 10:90 (mass ratio), 20:80 (mass ratio), and 30:70 (mass ratio) were obtained by the same method as in Example 1.

[0943] Using the obtained composition, substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 1. The results are shown in Table 3.

[0944] [Example 5]

[0945] Compound EOD-006 was used instead of compound EOD-005, and the substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 4. The results are shown in Table 3.

[0946] [Example 6]

[0947] Compound EOD-007 was used instead of compound EOD-005, and an ITO substrate was used instead of the substrate with the intermediate layer film. Polarization treatment was performed at 25V / μm. Otherwise, the substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 4. The results are shown in Table 3.

[0948] [Comparative Example 3]

[0949] Compound EOD-009 was used instead of compound EOD-005, and the substrate fabrication and electro-optic effect measurement were performed in the same manner as in Example 4. The results are shown in Table 3.

[0950] [Table 3]

[0951]

[0952] As can be clearly seen from Table 3, in Examples 4 to 6, even if the concentration of the nonlinear optical material increases, the increase in the electro-optic coefficient is greater than 1. Even if the nonlinear optical material is at a high concentration, the electro-optic coefficient continues to increase.

[0953] On the other hand, it can be seen that in Comparative Example 3, the increase in electro-optic coefficient from 20% to 30% mass is less than 1.0 (0.6), and the electro-optic coefficient no longer increases when the nonlinear optical material is at a high concentration.

[0954] The various embodiments have been described above, but it is self-evident that the present invention is not limited to these examples. Those skilled in the art will obviously conceive of various modifications or alterations within the scope of the claims, and it should be understood that these also fall within the technical scope of the present invention. Furthermore, the constituent elements of the above embodiments can be combined arbitrarily without departing from the spirit of the invention.

[0955] It should be noted that this application is based on Japanese patent application (Japanese Patent Application No. 2024-30022) filed on February 29, 2024, the contents of which are incorporated herein by reference.

[0956] Industrial availability

[0957] The compounds of this invention can be used in nonlinear optical elements, electric field sensors, etc.

Claims

1. A compound, said compound being represented by the following formula (1), [Chemical Formula 1] In equation (1), Z 11 The group is represented by the following formula (2). Z 12 The hydrocarbon group may be an aromatic group optionally having substituents or a branched, chain-like, or cyclic hydrocarbon group having 1 to 20 carbon atoms optionally having substituents, said hydrocarbon group optionally being saturated or unsaturated, and a portion of the hydrocarbon chain constituting said hydrocarbon group may optionally be substituted by at least one selected from oxygen, sulfur, nitrogen, and silicon atoms. Z 13 It is a divalent aromatic group that optionally has substituents. L 11 It is a divalent π-conjugated basis. A 11 The group is represented by formula (6) or formula (7) below. Z 12 With Z 13 They can be arbitrarily connected to form a ring structure. [Chemical Formula 2] In equation (2), R 21 The group is selected from the group consisting of alkyl groups optionally having substituents, aromatic groups optionally having substituents, amino groups optionally having substituents, halogen atoms, arylalkoxy groups optionally having substituents, arylalkyl groups optionally having substituents, alkoxy groups optionally having substituents, alkylthio groups optionally having substituents, arylalkylthio groups optionally having substituents, and silyl groups optionally having substituents. Ar 21 The group selected is from the group consisting of aromatic groups, hydrocarbon cyclic groups, and heterocyclic groups, optionally having a group other than R. 21 Other groups, * indicates the bonding position with N in equation (1). [Chemical Formula 3] In equation (6), * is the L in equation (1) 11 The bonding position, R 61 and R 62 Each of these groups is independently selected from the group consisting of alkyl groups optionally having substituents, aromatic groups optionally having substituents, halogen atoms, alkyl sulfonyl groups optionally having substituents, and aralkyl groups optionally having substituents. X 61 For O or S, [Chemical Formula 4] In equation (7), * is the L in equation (1) 11 The bonding position, R 73 It is a group selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an aromatic group optionally having a substituent, an acyl group optionally having a substituent, an alkoxycarbonyl group optionally having a substituent, and an aralkyl group optionally having a substituent.

2. The compound according to claim 1, wherein, Equation (2) is represented by the following equation (3), [Chemical Formula 5] In equation (3), R 31 and R 32 Each independently represents R in equation (2). 21 Groups with the same meaning Ar 33 The group selected is from the group consisting of aromatic groups, hydrocarbon cyclic groups, and heterocyclic groups, optionally having a group other than R. 31 and R 32 Other groups, * indicates the bonding position with N in equation (1).

3. The compound according to claim 1, wherein, Z in equation (1) 12 It is an alkyl group that optionally has substituents or an aromatic group that optionally has substituents.

4. The compound according to claim 1, wherein, Z in equation (1) 13 It is a divalent aromatic hydrocarbon group that optionally has substituents.

5. The compound according to claim 1, wherein, L in equation (1) 11 The group is represented by formula (4) or formula (5) below. [Chemical Formula 6] In equation (4), R 4a Each of the following groups is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an aromatic group optionally having a substituent, an amino group optionally having a substituent, a halogen atom, an alkoxy carbonyl group optionally having a substituent, an alkyl sulfonyl group optionally having a substituent, an aralkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aralkyl thio group optionally having a substituent. R 4b Each of the groups is independently selected from the group consisting of an alkyl group selected from hydrogen atoms, optionally having substituents, and optionally having substituents, an aromatic group. R 4c Each of the groups is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aromatic group optionally having a substituent. In addition, R 4a R 4b and R 4c They can be arbitrarily bonded together to form a ring. l is an integer from 0 to 5, n is an integer from 0 to 5, m is an integer from 0 to 5, and l + n + m > 0. [Chemical Formula 7] In equation (5), Ar 5 Each independently represents a divalent aromatic group optionally having substituents. R 5a Each of these groups is independently selected from the group consisting of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, and an aromatic group optionally having a substituent. Furthermore, in Ar... 5 In the case of substituents, the substituents and R 5a They can be arbitrarily bonded together to form a ring. e is an integer from 0 to 4, f is an integer from 0 to 5, and e + f > 0.

6. A nonlinear optically active polymer compound, wherein the nonlinear optically active polymer compound is formed by bonding a group obtained by removing at least one hydrogen atom from the compound according to claim 1 to a repeating unit in the polymer compound.

7. The nonlinear optically active polymer compound according to claim 6, wherein, The polymeric compound is selected from the group consisting of poly(meth)acrylate, polyvinyl chloride, polystyrene, polyimide, maleimide-styrene copolymer, maleimide-olefin copolymer, maleimide-methyl methacrylate copolymer, polycarbonate, and copolymers thereof.

8. A composition comprising at least one of the compounds according to any one of claims 1 to 5, a polymeric material, and a solvent; or comprising at least one of the nonlinear optically active polymeric compounds according to claim 6 and a solvent; or comprising at least one of the compounds according to any one of claims 1 to 5, at least one of the nonlinear optically active polymeric compounds according to claim 6, and a solvent.

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

10. A nonlinear optical element, said nonlinear optical element being made using the composition according to claim 8.

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

12. An optical modulator comprising the nonlinear optical element according to claim 10.

Images