Photoreactive polymers, monomers, optical films

Abstract

To provide a photoreactive polymer for an optical film exhibiting excellent refractive index anisotropy by polarized ultraviolet light irradiation or oblique incidence ultraviolet light irradiation, and heat calcination treatment dispensing with an oriented film, a monomer for the photoreactive polymer, and an optical film composed of the photoreactive polymer.SOLUTION: A photoreactive polymer has a constitutional unit including a photoreactive structure which reacts chemically by light irradiation, where the photoreactive structure is represented by the following formula (1). In the formula, a ring A, a ring B, and a ring C are independently an aromatic ring, a polycyclic aromatic ring, or a condensed ring-type aromatic ring each having an atom selected from the group consisting of C, N, O, and S as a ring constitutional atom, X is an alkoxy group, a halogen group, acyloxy group, or the like, Y is H, an alkoxy group, a halogen atom, acyloxy group, or the like, and S1 and S2 are independently a spacer group, or a single bond.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel polymer and its raw material monomer, and further to an optical film using the same. More specifically, it relates to a novel polymer and an optical film using the same that exhibits a high phase difference even in thin films upon ultraviolet light irradiation and heat treatment, such as a phase difference film suitable for liquid crystal display elements and organic EL. [Background technology]

[0002] Optical thin films, such as phase difference films, are used in various image display devices from the viewpoint of expanding the field of view. Existing phase difference films include thin films made by stretching resins, and examples of materials include polycarbonate resin, cyclic polyolefin, and cellulose acylate (see, for example, Patent Documents 1 to 3). However, stretched films have problems such as being prone to cracking and light leakage due to residual stress strain. In recent years, it has been proposed to use optically anisotropic layers using liquid crystalline compounds instead of stretched birefringent films. Such optically anisotropic layers require the provision of an alignment film on the support on which the optically anisotropic layer is formed in order to orient the liquid crystalline compound, and alignment films subjected to rubbing treatment or photo-alignment treatment are known (see, for example, Patent Documents 4 to 6). However, both require complex manufacturing equipment and processes, and there are also problems in terms of product yield. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2012-111964 [Patent Document 2] Japanese Patent Publication No. 2006-281628 [Patent Document 3] Japanese Patent Publication No. 2012-230282 [Patent Document 4] Japanese Patent Application Publication No. 8-160430 [Patent Document 5] Special Publication No. 2003-505561 [Patent Document 6] International Publication No. 2010-150748 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The present invention has been made in view of the above problems, and its objective is to provide an optical film made of a photoreactive polymer for optical films, a monomer for the photoreactive polymer, and a photoreactive polymer that does not require an alignment film and exhibits excellent refractive index anisotropy by polarized ultraviolet irradiation or oblique incident ultraviolet irradiation and heat firing treatment. [Means for solving the problem]

[0005] As a result of diligent research to solve the above problems, the inventors of the present invention have found that a photoreactive polymer having a specific structure can solve the above problems and can be used in optical films such as viewing angle compensation and liquid crystal alignment films, thus completing the present invention.

[0006] In other words, one aspect of the present invention is a photoreactive polymer in which a constituent unit including a photoreactive structure undergoes a chemical reaction upon light irradiation, wherein the photoreactive structure is represented by the following formula (1).

[0007] [ka]

[0008] [In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. R 1 and R 2This represents a group that may be the same or different from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group. X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. S 1 and S 2 Each of these independently represents a spacer group or a single bond. The spacer group represents a group selected from the group consisting of -CH2-, -CH2CH2-, -O-, -C(=O)-, -NH-, or alkylene groups having 3 to 20 carbon atoms, and two or more non-adjacent -CH2- in the alkylene group may each independently be replaced with -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-. n represents 0 or 1. Another aspect of the present invention relates to a monomer represented by the following formula (3). This monomer serves as a raw material for the photoreactive polymer of the present invention.

[0009] [ka]

[0010] [In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. R 1 and R 2 This represents a group that may be the same or different from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group. X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. F 1 and F 2 Each of these independently represents a group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, or an isocyanate group. n represents 0 or 1. Another aspect of the present invention relates to an optical film made of the photoreactive polymer. [Effects of the Invention]

[0011] Without requiring an alignment film, an optical film can be obtained consisting of a photoreactive polymer for optical films, a monomer for the photoreactive polymer, and a photoreactive polymer, exhibiting excellent refractive index anisotropy through polarized ultraviolet irradiation or oblique incident ultraviolet irradiation and heat firing treatment. [Modes for carrying out the invention]

[0012] The present invention will be described in detail below. The following descriptions of constituent elements may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In this specification, numerical ranges expressed using "from" mean a range that includes the numbers written before and after "from" as the lower and upper limits, respectively.

[0013] In this specification, structures enclosed in square brackets within a polymer structure represent repeating units within the polymer structure.

[0014] In this specification, the bonding orientation of the exemplified divalent groups and chemical structures (e.g., ester bonds and repeating units in polymer structures) is not particularly limited, as long as it is chemically acceptable.

[0015] A photoreactive polymer, which is one embodiment of the present invention, will be described in detail below.

[0016] One aspect of the present invention is a photoreactive polymer having a constituent unit that includes a photoreactive structure represented by formula (1) above (hereinafter referred to as "the polymer of the present invention").

[0017] In formula (1), rings A, B, and C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. These aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. Examples of substituents include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and halogen atoms.

[0018] In formula (1), at least one of ring A, ring B, and ring C is preferably a ring selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a phenanthrene ring, a chrysene ring, a triphenylene ring, a pyrene ring, a biphenyl ring, a terphenyl ring, a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, and an isoquinoline ring. From the viewpoint of ease of synthesis, a benzene ring, a naphthalene ring, a biphenyl ring, or a pyridine ring is preferable, and a ring selected from the group consisting of a benzene ring and a biphenyl ring is more preferable.

[0019] In formula (1), R 1 and R 2 may be the same or different and each represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group.

[0020] R 1 and R 2 The optionally substituted alkyl group having 1 to 20 carbon atoms represented by may be linear or branched and may be substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom.

[0021] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a hexyl group, an isohexyl group, a 1-methylpentyl group, a 1-ethylbutyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, and a 1,1,1,3,3,3-hexafluoroisopropyl group.

[0022] R 1 and R 2Examples of substituted carbon-3 to carbon-8 cycloalkyl groups represented by include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.

[0023] R 1 and R 2 Examples of substituted aromatic groups represented by include benzene rings, naphthalene rings, and biphenyl rings.

[0024] X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group.

[0025] Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group.

[0026] Examples of substituted C1 to C5 alkoxy groups include methoxy, ethoxy, methoxymethyloxy, ethoxymethyloxy, trifluoromethyloxy, 2,2-difluoroethyloxy, 2,2,2-trifluoroethyloxy, 2,2,3,3-tetrafluoropropyloxy, 2,2,3,3,3-pentafluoropropyloxy, and 1,1,1,3,3,3-hexafluoroisopropyloxy.

[0027] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0028] Examples of substituted acyloxy groups include acetyloxy, propionyloxy, butyryloxy, and valeryloxy groups.

[0029] Examples of alkylsulfonyloxy groups that may be substituted include alkylsulfonyloxy groups having 1 to 12 carbon atoms that may be substituted with fluorine, and more specifically, examples include methanesulfonyloxy groups, ethanesulfonyloxy groups, propanesulfonyloxy groups, trifluoromethanesulfonyloxy groups, etc.

[0030] Examples of substituted arylsulfonyloxy groups include benzenesulfonyl groups, p-toluenesulfonyloxy groups, and orthonitrobenzenesulfonyl groups.

[0031] Examples of substituted aryloxy groups include phenoxy, naphthyloxy, and anthracenyloxy groups.

[0032] Because of its excellent photoreactivity, X is preferably either a chlorine atom or a bromine atom.

[0033] S 1 and S 2 Each of these independently represents a spacer group or a single bond. The spacer group represents a group selected from the group consisting of -CH2-, -CH2CH2-, -O-, -C(=O)-, -NH-, or alkylene groups having 3 to 20 carbon atoms, and two or more non-adjacent -CH2- in the alkylene group may each independently be replaced with -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-.

[0034] n represents either 0 or 1.

[0035] In the polymer of the present invention, it is preferable that in formula (1), ring A, ring B, and ring C are rings selected from the group consisting of optionally substituted aromatic rings, optionally substituted polycyclic aromatic rings, or optionally substituted fused aromatic rings, with ring constituent atoms selected from the group consisting of carbon atoms and nitrogen atoms, and R 1 and R 2 However, the group may be the same or different, and is preferably selected from the group consisting of a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may be substituted. This results in a photoreactive polymer with liquid crystalline properties.

[0036] Examples of the photoreactive structure of the polymer of the present invention represented by general formula (1) include the structures represented by the following formulas (1-1) to (1-18).

[0037] [ka]

[0038] [In formulas (1-1) to (1-18), the ether bond may be replaced with a single bond, amide bond, imide bond, urethane bond, ester bond, etc.] The polymer of the present invention preferably further has repeating units represented by the following chemical formula (2).

[0039] [ka]

[0040] [In the formula, ring D represents a ring selected from the group consisting of an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, the ring constituent atoms being selected from the group consisting of an alicyclic hydrocarbon ring, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and these alicyclic hydrocarbon rings, aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. S 3 and S 4Each of these independently represents a spacer group or a single bond. The spacer group represents a group selected from the group consisting of -CH2-, -CH2CH2-, -O-, -C(=O)-, -NH-, or alkylene groups having 3 to 20 carbon atoms, and two or more non-adjacent -CH2- in the alkylene group may each independently be replaced with -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-. In formula (2), ring D represents a ring selected from the group consisting of an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, the ring constituent atoms being selected from the group consisting of an alicyclic hydrocarbon ring, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. These alicyclic hydrocarbon rings, aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents.

[0041] Specific examples of alicyclic hydrocarbon rings in ring D include the cyclohexane ring and the bicyclohexane ring.

[0042] Specific examples of aromatic rings in which ring D consists of atoms selected from the group comprising carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms include benzene, pyridine, pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, and triazole.

[0043] Examples of polycyclic aromatic rings that may have a carbon atom or substituent in ring D include biphenyl, terphenyl, bipyridine, bithiophene, and bifuran.

[0044] Examples of fused aromatic rings that may have substituents, with ring constituent atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms in ring D, include naphthalene, anthracene, phenanthrene, quinoline, benzofuran, benzimidazole, benzothiophene, indole, indazole, benzoxazole, benzothiazole, and benzotriazole.

[0045] For ring D, an aromatic ring is preferred in terms of availability, having atoms selected from the group consisting of alicyclic hydrocarbon rings, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms as ring constituent atoms, and a benzene ring, biphenyl ring, cyclohexane ring, or bicyclohexane ring is particularly preferred in terms of ease of introduction.

[0046] As a specific example of equation (2) above, the structures shown in equations (2-1-1) to (2-4-3) below can be exemplified.

[0047] [ka]

[0048] The polymer of the present invention may have structures derived from other compounds in addition to the photoreactive structures represented by formulas (1) and (2). Preferably, the structure derived from the other compound is derived from one or more compounds selected from the group consisting of dicarboxylic acids, dicarboxylic acid chlorides, diamines, tetracarboxylic dianhydrides, polyhydric hydroxy compounds, or isocyanate compounds. In particular, it is preferable that the structure is derived from at least one of dicarboxylic acids, dicarboxylic acid chlorides, or polyhydric hydroxy compounds.

[0049] Examples of specific polymers of the present invention include structures represented by the following formulas (P1-1-1-0) to (P1-18-1-4). Among the formulas (P1-1-1-0) to (P1-18-1-4), formulas (P1-1-1-0) to (P1-2-2-4) and (P1-11-1-0) to (P1-16-2-4) are preferred in that they exhibit good phase difference characteristics.

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[0068] The photoreactive polymer of the present invention is preferably used as a polymer obtained by performing ultraviolet irradiation (hereinafter sometimes referred to as light irradiation) treatment of either polarized ultraviolet light or obliquely incident ultraviolet light. Since a phase difference is produced by the light irradiation treatment, it can be suitably used as an optical component.

[0069] Examples of polymers obtained by light irradiation treatment include polymers containing the structure shown in the following formula (1').

[0070] [ka]

[0071] [In the formula, R 1 , R 2 A, B, C, Y, S 1 S 2 and n are R in formula (1) above, respectively. 1, R 2 A, B, C, Y, S 1 S 2 This is synonymous with n. As the constituent units represented by formula (1') are partially generated by light irradiation, the polymer chains in the parts excluding the constituent units represented by formula (1') undergo thermal orientation to avoid them.

[0072] Compounds exhibiting photofusion are disclosed in the reference (J. Chem. Soc., Chem. Commun., 1973, 647–648). The photoreactive polymer of this application uses monomers with a different structure from the compounds disclosed in the reference. Specifically, a polymer having a photoreactive unit represented by formula (1) has been found to be obtained by copolymerizing the monomers, and it has been found that even in the polymer state, it is exposed to ultraviolet light to give a fused ring portion represented by formula (1'), and the remaining polymer chain portion that did not undergo photofusion undergoes thermal orientation. This results in an effect of increased birefringence.

[0073] The polymer having the constituent unit represented by formula (1) above may be a resin composition containing other polymers, surfactants, plasticizers, ultraviolet absorbers, antioxidants, polymer electrolytes, conductive complexes, inorganic fillers, pigments, antistatic agents, antiblocking agents, lubricants, etc., to the extent that it does not exceed the spirit of the invention.

[0074] The polymer manufacturing method and the monomers used in the polymer manufacturing method of the present invention are described below.

[0075] The polymer of the present invention can be produced, for example, by copolymerizing a monomer represented by the following formula (3) (hereinafter also referred to as "the monomer of the present invention"). The copolymerization method is not particularly limited, and examples of polymerization methods known in the art include solution polymerization, melt polymerization, and interfacial polymerization.

[0076] [ka]

[0077] [In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. R 1 and R 2 This represents a group that may be the same or different from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group. X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. F 1 and F 2 Each of these independently represents a group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, or an isocyanate group. n represents 0 or 1. In formula (3), rings A, B, and C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. These aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. Examples of substituents include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and halogen atoms.

[0078] In formula (3), at least one of rings A, B, and C is preferably a ring selected from the group consisting of a benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, phenanthrene ring, chrysene ring, triphenylene ring, pyrene ring, biphenyl ring, terphenyl ring, furan ring, thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, quinoline ring, and isoquinoline ring. A benzene ring, naphthalene ring, biphenyl ring, or pyridine ring is preferred for ease of synthesis, and a ring selected from the group consisting of a benzene ring and a biphenyl ring is even more preferred.

[0079] In formula (3), R 1 and R 2 This represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group, which may be the same or different in nature.

[0080] R 1 and R 2 The optionally substituted alkyl group having 1 to 20 carbon atoms, represented by , may be linear or branched, and may be substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom.

[0081] Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 1-ethylbutyl group, trifluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, and 1,1,1,3,3,3-hexafluoroisopropyl group.

[0082] R 1 and R2 Examples of substituted carbon-3 to carbon-8 cycloalkyl groups represented by include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.

[0083] R 1 and R 2 Examples of substituted aromatic groups represented by include benzene rings, naphthalene rings, and biphenyl rings.

[0084] X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group.

[0085] Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group.

[0086] Examples of substituted C1 to C5 alkoxy groups include methoxy, ethoxy, methoxymethyloxy, ethoxymethyloxy, trifluoromethyloxy, 2,2-difluoroethyloxy, 2,2,2-trifluoroethyloxy, 2,2,3,3-tetrafluoropropyloxy, 2,2,3,3,3-pentafluoropropyloxy, and 1,1,1,3,3,3-hexafluoroisopropyloxy.

[0087] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0088] Examples of substituted acyloxy groups include acetyloxy, propionyloxy, butyryloxy, and valeryloxy groups.

[0089] Examples of alkylsulfonyloxy groups that may be substituted include alkylsulfonyloxy groups having 1 to 12 carbon atoms that may be substituted with fluorine, and more specifically, examples include methanesulfonyloxy groups, ethanesulfonyloxy groups, propanesulfonyloxy groups, trifluoromethanesulfonyloxy groups, etc.

[0090] Examples of substituted arylsulfonyloxy groups include benzenesulfonyl groups, p-toluenesulfonyloxy groups, and orthonitrobenzenesulfonyl groups.

[0091] Examples of substituted aryloxy groups include phenoxy, naphthyloxy, and anthracenyloxy groups.

[0092] Because of its excellent photoreactivity, X is preferably either a chlorine atom or a bromine atom.

[0093] In formula (3), F 1 and F 2 Each of these independently represents a group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, or an isocyanate group. 1 and F 2 Preferably, it is a hydroxyl group.

[0094] n represents either 0 or 1.

[0095] In formula (3), it is preferable that rings A, B, and C are rings selected from the group consisting of optionally substituted aromatic rings, optionally substituted polycyclic aromatic rings, or optionally substituted fused aromatic rings, with ring constituent atoms selected from the group consisting of carbon atoms and nitrogen atoms, and R 1 , R 2However, it is preferable that the group is selected from the group consisting of a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may be substituted. This results in a photoreactive polymer having liquid crystalline properties.

[0096] The monomer represented by formula (3) is preferably a compound represented by the following formula (3-1).

[0097] [ka]

[0098] [In the formula, R 1 A, B, X, Y, F 1 and F 2 These are the R values ​​in equation (3) above, respectively. 1 A, B, X, Y, F 1 and F 2 This is synonymous with [the above]. The monomer represented by formula (3) is preferably one of the monomers represented by the following formulas (3-1-1) to (3-1-9) and (3-2-1).

[0099] [ka]

[0100] [In the formula, R 1 and R 2 This represents a group that may be the same or different from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group. X a This represents a group selected from the group consisting of a halogen atom, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, or an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms. Y a represents a hydrogen atom or a halogen atom. F 1a and F 2aEach of these independently represents either a hydroxyl group or an amino group. As the monomer represented by formula (3) above, a monomer represented by any of the following formulas (3-1-1-1) to (3-2-1-3) is more preferred.

[0101] [ka]

[0102] [In the formula, R 1 and R 2 This represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group, which may be the same or different in nature. Specific examples of the monomer represented by formula (3) include the structures shown in formulas (3-1-1-1-1) to (3-2-1-3-2) below. Among formulas (3-1-1-1-1) to (3-2-1-3-2), formulas (3-1-1-1-1) to (3-1-1-1-4) and (3-1-7-1-1) to (3-1-9-3-1) are preferred because they exhibit good phase difference characteristics.

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[0108] The polymer of the present invention is preferably synthesized by copolymerizing the monomer represented by formula (3) with one or more copolymerization monomers arbitrarily selected from the group consisting of the corresponding dicarboxylic acid, dicarboxylic acid chloride, diamine, tetracarboxylic dianhydride, polyvalent hydroxy compound, or isocyanate compound, and is particularly preferably copolymerized with at least one of dicarboxylic acid chloride or polyvalent hydroxy compound.

[0109] For example, when producing the polymer of the present invention by solution polymerization, the polymer can be easily obtained by interfacial polymerization of the monomer of the present invention having a diol structure and a copolymerization monomer in a two-layer system of water and an organic solvent under basic conditions.

[0110] Dicarboxylic acids can be selected without limitation from known dicarboxylic acids, and examples include aliphatic polycarboxylic acids (specifically saturated polycarboxylic acids with 2 to 20 carbon atoms such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid, and unsaturated polycarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, and itaconic acid), alicyclic polycarboxylic acids (cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, etc.), and aromatic polycarboxylic acids (terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-oxybis(benzoic acid), 2,5-franzicarboxylic acid, etc.).

[0111] The dicarboxylic acid dichloride used in the present invention can be selected without limitation from known dicarboxylic acid dichlorides.

[0112] Examples of dicarboxylic acid dichlorides include saturated carboxylic acid dichlorides with 2 to 20 carbon atoms, such as oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, and sebacate acid dichloride; unsaturated polycarboxylic acid dichlorides, such as fumaric acid dichloride and itaconic acid dichloride; aliphatic carboxylic acid dichlorides, such as cyclobutanedicarboxylic acid dichloride, cyclopentanedicarboxylic acid dichloride, and cyclohexanedicarboxylic acid dichloride; and aromatic polycarboxylic acids, such as terephthalic acid dichloride, isophthalic acid dichloride, orthophthalic acid dichloride, 4,4'-biphenyldicarboxylic acid dichloride, 4,4'-oxybis(benzoic acid chloride), and 2,5-franzicarboxylic acid dichloride.

[0113] The polyhydric hydroxy compound used in the present invention can be selected without limitation from known polyhydric hydroxy compounds.

[0114] Examples of polyvalent hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,2-propylene glycol, 1,4-butanediol, 2,2-butanediol, 2,3-butanediol, 2,4-dimethyl-2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-heptanediol, and cyclopene. Tanediol, cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydroquinone, tetramethylhydroquinone, 4,4'-dihydroxybiphenyl, benzenedimethanol, vanillyl alcohol, frangimethanol, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-(1,3-dimethylbutylidene)diphenol, 6,6'-dihydroxy-4,4,4',4',7,7'-hexamethyl-2,2'-spirobyl Chroman, tricyclodecanedimethanol, 2,2'-dihydroxydiphenyl ether, 4,4'-methylenebis(2,6-dimethylphenol), 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2-butene-1,4-diol, 2,2-diisobutyl-1,3-propanediol, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-bis(3- Hydroxyphenoxy)benzene, 4,4'-bicyclohexanol, bis(4-hydroxy-3-methylphenyl) sulfide, 2,2-diisoamyl-1,3-propanediol, 4,4'-dihydroxydiphenylmethane, dihydroxynaphthalene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, 1,4-benzenedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5] Undecane, 4,4'-biphenyldimethanol, 1,3-bis(hexafluoro-α-hydroxyisopropyl)benzene, 3,6-dihydroxybenzonorbornane, 2-benzyloxy-1,3-propanediol, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl ether, 9,9-bis(4-hydroxyphenyl)fluorene, 1,8-bis(hydroxymethyl)anthracene, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl ]Benzene, α,α'-bis(4-hydroxy-3,5-dimethylphenyl)-1,4-diisopropylbenzene, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2'-methylenebis(4-methylphenol), 1,3-bis(4-hydroxyphenoxy)benzene, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, Examples of divalent hydroxy compounds include 2,2'-dihydroxybenzophenone, 2,2'-bis(hydroxymethyl)diphenyl ether, 7,7'-dihydroxy-4,4,4',4'-tetramethyl-2,2'-spirovichroman, 1,4-bis(hydroxymethyl)-2,3,5,6-tetramethylbenzene, 4,4'-ethylidenebisphenol, cyclohexanedimethanol, polyethylene glycol, 1,3-adamantanediol, 1-hydroxy-3-(hydroxymethyl)adamantane, 2,7-dihydroxy-9H-fluoren-9-one, and polyethylene glycol of various molecular weights; trivalent hydroxy compounds include glycerin, trimethylolpropane, triethanolamine, 2,3,4,4'-tetrahydroxybenzophenone, 1,2,3-butanetriol, and 2,6-bis(hydroxymethyl)-4-methylphenol; and tetravalent hydroxy compounds include pentaerythritol. Other polyvalent hydroxy compounds include various sugars.

[0115] The diamine used in the present invention can be selected without limitation from known diamines.

[0116] Examples of diamines include ethylenediamine, 1,2-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,4-bis(aminomethyl)cyclohexane, cyclohexanediamine, 3,3'-diamino-N-methyldipropylamine, 1,12-dodecanediamine, 1,4-phenylenediamine, 2-methyl-1,3-propanediamine, 1,10-decanediamine, 2,2'-oxybis(ethylamine), 1,8-octanediamine, 3-aminobenzylamine, and 4-amino Examples include benzylamine, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 2,2-dimethyl-1,3-propanediamine, 2,2'-thiobis(ethylamine), 2-methyl-1,5-diaminopentane, diethylene glycol bis(3-aminopropyl) ether, 1,11-undecanediamine, 2,2'-diamino-N-methyldiethylamine, 1,3-phenylenediamine, 1,3-propanediamine, bis(aminomethyl)norbornane, m-xylylenediamine, 1,2-bis(2-aminoethoxy)ethane, isophoronediamine, and 1,4-butanediol bis(3-aminopropyl) ether.

[0117] The tetracarboxylic dianhydride used in the present invention can be selected without limitation from known tetracarboxylic dianhydrides.

[0118] Examples of tetracarboxylic dianhydrides include pyromellitic anhydride, dibromopyromellitic anhydride, 3,4'-biphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, octahydrobiphenylene-4a,8b:4b,8a-tetracarboxylic dianhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3,4'-biphthalic anhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-biphthalic anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and bis(1,3-dioxo-1,3-dihydroisobenzofuran-5) -carboxylic acid) 1,4-phenylene, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 4,4'-(ethyn-1,2-diyl)diphthalic anhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, bicyclo[2.2.2] Octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride Examples include aqueous solutions, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 4,4'-biphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic acid, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride.

[0119] The diisocyanate used in the present invention can be selected without limitation from known diisocyanates.

[0120] The isocyanate compounds used in the present invention are not particularly limited and include, for example, aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds (monocyclic alicyclic isocyanate compounds, crosslinked cyclic alicyclic isocyanate compounds), and polyisocyanate derivatives thereof.

[0121] Examples of aromatic isocyanate compounds include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or mixtures thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate, or mixtures thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or mixtures thereof) (XDI), and tetramethylxylylene Examples include isocyanates (1,3- or 1,4-tetramethylxylylene diisocyanate, or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanates (1,5-, 1,4- or 1,8-naphthalene diisocyanate, or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc.

[0122] Examples of aliphatic isocyanate compounds include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and the like.

[0123] Examples of monocyclic alicyclic isocyanate compounds include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate), or mixtures thereof). Examples include hydrogenated MDI (compound), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane, or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), etc.

[0124] Examples of cross-linked cyclic alicyclic isocyanate compounds include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane.

[0125] Any solvent that does not harm the reaction can be used as the solvent for producing the polymer of the present invention. Examples include ether-based solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, dimethoxyethane, tetrahydrofuran (THF), and dioxane; nitrile-based solvents such as acetonitrile and propionitrile; aromatic-based solvents such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; amide-based solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; halogen-based solvents such as dichloromethane, chloroform, and carbon tetrachloride; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; acetic acid, dimethyl sulfoxide (DMSO), and water. These solvents may be used individually or in any ratio of two or more.

[0126] When the polymer of the present invention is subjected to interfacial polymerization in a two-layer system of water and an organic solvent, a phase transfer catalyst may be used to promote the reaction. Examples of phase transfer catalysts include ammonium salts such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraamylammonium chloride, tetraamylammonium bromide, tetraheptylammonium chloride, tetraheptylammonium bromide, dimethyldipalmitylammonium chloride, and dimethyldipalmitylammonium bromide; phosphonium salts such as tetraethylphosphonium chloride, tetraethylphosphonium bromide, tributylhexylphosphonium chloride, tributylhexylphosphonium bromide, tetra-n-octylphosphonium chloride, tetra-n-octylphosphonium bromide, tributyl-n-octylphosphonium chloride, tributyl-n-octylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, and tetraphenylphosphonium chloride.

[0127] When the polymer of the present invention is subjected to interfacial polymerization in a two-layer system of water and an organic solvent, it is desirable to use a base to promote the reaction. Examples of bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, and tetrabutylammonium hydroxide.

[0128] The method for producing the monomer of the present invention will be described below.

[0129] The monomer of the present invention, represented by formula (3), is the F compound represented by the following formula (3'). 3 and F 4 F 1 and F 2 It can be manufactured by a manufacturing method that includes a step of converting to [a specific type of product].

[0130] [ka]

[0131] [In the formula, R 1 , R 2 A, B, C, X, Y, n, F 1 and F 2 These are the R values ​​in equation (3) above, respectively. 1 , R 2 A, B, C, X, Y, n, F 1 and F 2 It is synonymous with F 3 and F 4 Each of these independently represents a group selected from the group consisting of methoxy, methoxymethyloxy, benzyloxy, hydroxy, amino, carboxy, isocyanate, and nitro groups, and at least one of them is a group selected from the group consisting of methoxy, methoxymethyloxy, benzyloxy, and nitro groups. The monomers of the present invention can be synthesized by combining general techniques in organic synthesis chemistry.

[0132] For example, in (3') above, if n=0, the monomer of the present invention is F of the amide compound represented by formula (3-1'). 3 and F 4 F 1 and F 2 It can be manufactured by converting it to [a specific form of].

[0133] [ka]

[0134] [In the formula, R 1 A, B, X, Y, F 1 and F 2 These are the R values ​​in equation (3) above, respectively. 1 A, B, X, Y, F 1 and F 2 It is synonymous with F 3 and F 4is respectively the F in the above formula (3’) 3 and F 4 are synonymous.] Furthermore, the monomer of the present invention represented by the formula (3-1-A) can be produced by converting the F of the amide compound represented by the formula (3-1-A’) into a hydroxy group. 3a It can be produced by converting it into a hydroxy group.

[0135]

Chemical formula

[0136] [In the formula, F 3a is respectively independently a hydroxy group, a methoxy group, a methoxymethyloxy group, or an optionally substituted benzyloxy group, and represents a group that is not a hydroxy group at the same time.] Examples of the method for converting a methoxy group into a hydroxy group include conversion with boron tribromide, conversion with aluminum chloride, and conversion with pyridinium chloride. Among them, conversion with boron tribromide is more preferable because it proceeds under mild conditions.

[0137] The methoxymethyloxy group can be converted into a hydroxy group under strongly acidic conditions. For deprotection under strongly acidic conditions, trifluoroacetic acid (TFA), hydrochloric acid, or sulfuric acid can be used.

[0138] The benzyloxy group can be converted into a hydroxy group by reduction using a Pd / C catalyst, Raney nickel, etc. in a hydrogen gas atmosphere.

[0139] Furthermore, the amide compound represented by the formula (3-1’) can be produced by a condensation reaction between a carboxylic acid derivative represented by the following formula (4) and an amine compound represented by the following formula (5).

[0140]

Chemical formula

[0141] [In the formula, R1 , A, B, X, and Y are each R in the formula (3) 1 , which is synonymous with A, B, X, and Y. F 3 and F 4 are each F in the formula (3’) 3 and F 4 and are synonymous with it. Q represents a leaving group.] Q represents a leaving group, and examples thereof include a hydroxy group, a chlorine atom, and a bromine atom. Among them, a hydroxy group and a chlorine atom are preferred, and a chlorine atom is particularly preferred.

[0142] When Q in the formula is a chlorine atom or a bromine atom, a condensation reaction can be carried out in the presence of a base.

[0143] Examples of the base used in the condensation reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal hydrides such as sodium hydride, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, amines such as triethylamine, N,N - diisopropylethylamine, pyridine, 4 - dimethylaminopyridine, 1,4 - diazabicyclo[2.2.2]octane, diazabicycloundecene, and tetrabutylammonium hydroxide.

[0144] The amount of the base used in the condensation reaction is not particularly specified, and any amount that can neutralize the acid generated during the reaction may be used.

[0145] Furthermore, if Q in the formula is a hydroxyl group, a condensing agent can be used in the reaction. The condensing agent used in the present invention can be any agent capable of forming the above-mentioned amide bond, and commonly used condensing agents can be used. Specifically, as condensing agents, 1H-benzotriazole-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP), 1-hydroxybenzotriazole (HOBt), 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate (PyBOP), N,N-dicyclohexylcarbodiimide (DCC), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide (EDC) or its hydrochloride, N,N'-diisopropylcarbodiimide (DIC), 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride (DMT-MM), O-(benzotriazole-1-yl)-N,N,N',N')-tetramethyluronium hexafluorophosphate (HBTU), etc., can be used.

[0146] Furthermore, the amide compound represented by formula (3-1') has a hydrogen atom on the nitrogen atom of the amide group adjacent to ring B of the amide compound represented by formula (3-1'') below. 1 It can also be synthesized by substitution.

[0147] [ka]

[0148] [In the formula, R 1 A, B, X, and Y are R in formula (3) above, respectively. 1 This is synonymous with A, B, X, and Y. F 3 and F 4 These are F in equation (3') above, respectively. 3 and F 4 This is synonymous with [the above]. For example, the monomer of the present invention represented by formula (3-2-A) can be produced by a condensation reaction between a dicarboxylic acid or its derivative represented by formula (7) and an amine compound represented by formula (8).

[0149] [ka]

[0150] [In the formula, R 1 A, B, X, and Y are R in equation (1) above, respectively. 1 This is synonymous with A, B, X, and Y. Q represents a leaving group. The condensation reaction can be carried out using the same method as the method used to produce the amide compound shown in formula (3') above.

[0151] The photoreactive polymer of the present invention can be used as an optical film (hereinafter also referred to as "the film of the present invention"). There are no particular limitations on the method for producing the film of the present invention, and examples include melt deposition methods and solution casting methods.

[0152] <Fat-melt film formation method> Methods for melt-forming films include, but are not limited to, melt extrusion using a T-die, calendering, hot pressing, co-extrusion, co-melting, multi-layer extrusion, and inflation molding.

[0153] <Solution Casting Method> Solution casting is a method for obtaining a thin film by casting a solution of polymer dissolved in a solvent (hereinafter referred to as "casting dope") onto a support substrate, and then removing the solvent by heating or other means. Methods for casting the casting dope onto the support substrate include spin coating, T-die method, doctor blade method, bar coater method, roll coater method, and lip coater method. Industrially, the most common method involves continuously extruding the casting dope from a die onto a belt-shaped or drum-shaped support substrate. Examples of support substrates used include glass substrates, metal substrates such as stainless steel and ferrotype, and films such as polyethylene terephthalate.

[0154] <Surfactants> The film of the present invention may contain at least one surfactant in order to reduce film thickness unevenness. Examples of surfactants that can be contained include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, etc. Among them, fluorine-containing surfactants are particularly preferred.

[0155] As described above, the film of the present invention can be suitably used as an optical film, and particularly since it exhibits a phase difference, it can be suitably used as a retardation film.

[0156] The film of the present invention exhibits a phase difference by light irradiation. Examples of the light for irradiation include ultraviolet rays, and particularly, polarized ultraviolet rays or obliquely incident ultraviolet rays can be exemplified. When using ultraviolet rays, the wavelength of the ultraviolet rays is appropriately selected from the range of 200 nm or more and 400 nm or less. The irradiation energy amount is preferably 10 mJ / cm 2 or more and 10000 mJ / cm 2 or less.

[0157] After performing the above light irradiation, the film of the present invention is further heat-treated. Thereby, the photoreactive polymer of the present invention exhibits a phase difference. Examples of the heat treatment temperature include 50°C or more and 400°C or less.

[0158] By performing polarized ultraviolet ray irradiation or obliquely incident ultraviolet ray irradiation on the film of the present invention and further performing a heat baking treatment, three-dimensional refractive index anisotropy is exhibited, and it can be used as a retardation film.

[0159] The film of the present invention, by light irradiation and heat baking treatment, has a retardation (Re) represented by the following mathematical formula (A) measured using a light source of 589 nm, which is 1 nm or more, preferably 1 to 300 nm, and particularly preferably 1 to 200 nm.

[0160] Re = (ny - nx) × d (A) [In Equation (A), nx represents the refractive index in the in-plane phase axis direction (the direction with the lowest refractive index) of the film, ny represents the refractive index in the in-plane retardation axis direction (the direction with the highest refractive index) of the film, and d represents the film thickness.] When the film of the present invention is used as a retardation film, it may be used as a single film or as a multilayer film in which other films are laminated.

[0161] Since the film of the present invention has excellent liquid crystal alignment properties, it can be suitably used as a member constituting a liquid crystal alignment film.

Example

[0162] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited thereto.

[0163] <Polarized ultraviolet irradiation> Using an ultra-high pressure mercury lamp source (manufactured by Asahi Spectra Co., Ltd., product name: REX-250) incorporated with a band-pass filter (248 nm or 313 nm), only P-polarized light was extracted using a polarization beam splitter with the corresponding wavelength and irradiated.

[0164] <Heat baking treatment> The heat baking treatment was performed using a thermostatic oven with a safety door (manufactured by ESPEC, product name: SPH-202).

[0165] <Measurement of retardation characteristics> Using a sample tilt type automatic birefringence meter (manufactured by AXOMETRICS, product name: AxoScan), the retardation characteristics of the retardation film were measured using light with a wavelength of 589 nm.

[0166] <Measurement of film thickness of thin film> The film thickness of the thin film was measured using a spectroscopic ellipsometer (manufactured by J.A. Woollam Co., Ltd., product name: RC2-U).

[0167] [Monomer Example 1]

[0168] [ka]

[0169] Under an argon atmosphere, thionyl chloride (15.5 mL) and DMF (250 μL) were added to a solution of 2-chloro-4-methoxybenzoic acid (5.00 g, 26.8 mmol) in toluene (25 mL), and the mixture was stirred at 100 °C for 1 hour. After that, the thionyl chloride was removed under reduced pressure, and THF (45 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0170] A solution of 4-(methylamino)phenol sulfate (4.61 g, 13.4 mmol) in THF (45 mL) and water (45 mL) was cooled to 0°C. Sodium bicarbonate (5.63 g, 67.0 mmol) was added while stirring, and then the previously prepared THF solution of acid chloride was added dropwise over 5 minutes. The mixture was heated to room temperature and stirred vigorously for 1.5 hours, after which concentrated hydrochloric acid (10 mL) was added and the mixture was concentrated under reduced pressure. After filtering out the solid formed in the system, the crude solid was obtained by washing with water (200 mL). This was further purified by reprecipitation (hexane: 50 mL, ethyl acetate: 5 mL, ethanol: 3 mL) to obtain a white solid of 2-chloro-4'-hydroxy-4-methoxy-N-methylbenzanilide (yield: 6.42 g, yield: 82%). 1 H-NMR(400MHz,DMSO-d6):δ9.50(brs,1H),7.16(d,J=8.6Hz,1H),6.99(d,J=8.7Hz,2H),6.85( d,J=2.4Hz,1H),6.73(dd,J=8.6,2.4Hz,1H),6.56(d,J=8.7Hz,2H),3.69(s,3H),3.28(s,3H). Under an argon atmosphere, a suspension of 2-chloro-4'-hydroxy-4-methoxy-N-methylbenzanilide (5.00 g, 17.1 mmol) in dichloromethane (170 mL) was cooled to 0°C, and then 1 M boron tribromide dichloromethane solution (68.4 mL, 68.4 mmol) was added dropwise over 15 minutes. The reaction system was raised to room temperature, stirred for 13 hours, and then cooled again to 0°C. After adding ice (400 g), the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure to remove the dichloromethane, and then extracted with ethyl acetate (200 mL x 3). The resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 5:95), and then dried under reduced pressure (120°C, vacuum pump) to obtain a white solid of 2-chloro-4,4'-dihydroxy-N-methylbenzanilide (compound 1) (yield: 3.67 g, yield: 77%). 1 H-NMR (400MHz, DMSO-d6): δ10.4-9.15(br,2H),7.02(m,1H),6.95(d,J=8.5Hz,2H),6.61(m,1H),6.56(d,J=8.5Hz,2H),6.53(m,1H),3.27(s,3H). [Monomer Example 2]

[0171] [ka]

[0172] Under an argon atmosphere, thionyl chloride (15.5 mL) was added to a toluene (20 mL) solution of 2-chloro-3-methoxybenzoic acid (4.00 g, 21.4 mmol), and the mixture was stirred at 100°C for 1 hour. Then, thionyl chloride was removed by distillation using a Dean-Stark apparatus (oil bath, 120°C), and THF (40 mL) was added to the resulting residue. This entire solution was used in the next reaction. A THF (36 mL)-water (36 mL) solution of 4-(methylamino)phenol sulfate (3.69 g, 10.7 mmol) was cooled to 0°C, and sodium bicarbonate (4.49 g, 53.5 mmol) was added while stirring. Then, the previously prepared THF solution of acid chloride was added dropwise over 5 minutes. The mixture was heated to room temperature and vigorously stirred for 1 hour, then concentrated hydrochloric acid (8 mL) was added, and the mixture was concentrated under reduced pressure. After filtering out the solid formed in the system, washing with water (200 mL) yielded a white solid of 2-chloro-4'-hydroxy-3-methoxy-N-methylbenzanilide (yield: 6.11 g, yield: 98%). 1 H-NMR (400MHz, DMSO-d6): δ9.48(brs,1H),7.12(dd,J=8.3,7.7Hz,1H),7.01(d,J=8.8Hz,2H),6.93( dd,J=8.3,1.3Hz,1H),6.82(dd,J=7.7,1.3Hz,1H),6.55(d,J=8.8Hz,2H),3.76(s,3H),3.28(s,3H). Under an argon atmosphere, a suspension of 2-chloro-4'-hydroxy-3-methoxy-N-methylbenzamide (500 mg, 1.71 mmol) in dichloromethane (18 mL) was cooled to 0 °C, and then a 1 M boron tribromide dichloromethane solution (6.84 mL, 6.84 mmol) was added dropwise over 5 minutes. After the reaction system was warmed to room temperature, it was stirred for 1.5 hours and then cooled to 0 °C again. Ice (50 g) and 2 N hydrochloric acid (30 mL) were added, and the mixture was stirred at room temperature until the ice dissolved. Dichloromethane was distilled off by concentrating the mixture under reduced pressure, and then the mixture was extracted with ethyl acetate (20 mL × 3) and washed with saturated brine (20 mL). The obtained organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography (hexane:ethyl acetate = 5:95) and then dried under reduced pressure (120 °C, vacuum pump) to obtain a white solid of 2-chloro-3,4'-dihydroxy-N-methylbenzamide (Compound 2) (yield: 330 mg, yield: 70%). 1 1H-NMR (400 MHz, DMSO-d6): δ 10.2 (brs, 1H), 9.50 (brs, 1H), 7.00 (d, J = 8.8 Hz, 2H), 6.94 (t, J = 7.8 Hz, 1H), 6.74 (dd, J = 8.1, 1.3 Hz, 1H), 6.64 (m, 1H), 6.55 (d, J = 8.8 Hz, 2H), 3.27 (s, 3H). [Monomer Example 3]

[0173] [[ID=۸]]

Chemical Structure

[0174] Under an argon atmosphere, thionyl chloride (19.4 mL) was added to a solution of 2-chloro-5-methoxybenzoic acid (5.00 g, 26.8 mmol) in toluene (25 mL), and the mixture was stirred at 100 °C for 1.5 hours. Then, thionyl chloride was distilled off using a Dean-Stark apparatus (oil bath at 120 °C), and THF (40 mL) was added to the obtained residue. This solution was used in its entirety for the next reaction.

[0175] A solution of 4-(methylamino)phenol sulfate (4.61 g, 13.4 mmol) in THF (45 mL) and water (45 mL) was cooled to 0°C. Sodium bicarbonate (5.63 g, 67.0 mmol) was added while stirring, and then the previously prepared THF solution of acid chloride was added dropwise over 10 minutes. The mixture was heated to room temperature and vigorously stirred for 1.5 hours, after which concentrated hydrochloric acid (10 mL) was added and the mixture was concentrated under reduced pressure. After filtering the solid formed in the system, it was washed with water (200 mL) to obtain a white solid of 2-chloro-4'-hydroxy-5-methoxy-N-methylbenzanilide (yield: 7.07 g, yield: 90%). 1 H-NMR(400MHz,DMSO-d6):δ9.56(brs,1H),7.15(d,J=8.8Hz,1H),7.05(d,J=8.8Hz,2H),6.86( d,J=3.0Hz,1H),6.76(dd,J=8.8,3.0Hz,1H),6.57(d,J=8.8Hz,2H),3.65(s,3H),3.29(s,3H). Under an argon atmosphere, a suspension of 2-chloro-4'-hydroxy-5-methoxy-N-methylbenzanilide (5.00 g, 17.1 mmol) in dichloromethane (175 mL) was cooled to 0°C, and then 1 M boron tribromide dichloromethane solution (68.6 mL, 68.6 mmol) was added dropwise over 30 minutes. The reaction system was raised to room temperature, stirred for 21 hours, and then cooled again to 0°C. After adding ice (300 g) and 2 M hydrochloric acid (300 mL), the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure to remove the dichloromethane, extracted with ethyl acetate (100 mL x 3), and then washed with water (100 mL). The resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The resulting residue was purified by silica gel chromatography (hexane:ethyl acetate = 10:90) to obtain 2-chloro-4',5-dihydroxy-N-methylbenzanilide (compound 3) as a white solid (yield: 3.94 g, yield: 83%). 1 H-NMR (400MHz, DMSO-d6): δ9.69(brs,1H),9.50(brs,1H),7.06-6.97(m,3H),6.61-6.54(m,4H),3.27(s,3H). [Monomer Example 4]

[0176] [ka]

[0177] Under an argon atmosphere, thionyl chloride (19.4 mL, 0.27 mol) and DMF (250 μL) were added to a toluene solution (25 mL) of 2-chloro-4-methoxybenzoic acid (5.00 g, 26.8 mmol) and heated under reflux for 1.5 hours. After the reaction was complete, the solvent was concentrated under reduced pressure, and the solvent was further removed by azeotropic distillation with THF. After vacuum drying, the mixture was purged with argon, and the resulting acid chloride was prepared in a THF solution (45 mL).

[0178] Under an argon atmosphere, sodium bicarbonate (5.63 g, 67.0 mmol) was added to a mixed solution of 4-methoxyaniline (3.30 g, 26.8 mmol) in THF (45 mL) and water (45 mL) under ice cooling, and the THF solution of the acid chloride prepared above was slowly added dropwise. After the addition, the temperature was raised to room temperature and the mixture was stirred at room temperature for 17 hours. After the reaction was complete, the solvent was concentrated under reduced pressure, and water (200 mL) was added to the resulting crude product. After stirring for a while, the solid was filtered off and washed with water (750 mL), 2N hydrochloric acid (100 mL x 3) and water (250 mL x 3) to obtain a white solid of 2-chloro-4,4'-dimethoxybenzanilide (yield: 7.57 g, yield: 97%). 1 H-NMR (400MHz, DMSO-d6): δ8.03(brs,1H),7.78(d,J=8.7Hz,1H),7.56-7.52(m,2H),6.94-6.86(m,4H),3.84(s,3H),3.81(s,3H). Under an argon atmosphere, 55% sodium hydride (760 mg, 17.5 mmol) and 1-iodobutane (1.78 mL, 15.4 mmol) were added to a DMF solution (21 mL) of 2-chloro-4,4'-dimethoxybenzanilide (3.00 g, 10.3 mmol) under ice cooling. The mixture was then heated to room temperature and stirred for 3 hours and 30 minutes. After the reaction was complete, the mixture was cooled on ice, and ammonium chloride aqueous solution (120 mL) was added to the reaction solution. The mixture was extracted with ethyl acetate (50 mL x 2), washed with water (30 mL x 2) and saturated brine (30 mL x 1), dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 2:1) to quantitatively obtain 3.58 g of N-butyl-2-chloro-4,4'-dimethoxybenzanilide as a yellow viscous substance. 1 H-NMR (400MHz, CDCl3): δ7.01(d,J=8.8Hz,2H),6.97(d,J=8.5Hz,1H),6.71(d,J=2.4Hz,1H),6.69(d,J=8.8Hz,2H),6.56(dd,J=8. 5,2.4Hz,1H),3.88-3.84(m,2H),3.72(s,3H),3.70(s,3H),1.63-1.55(m,2H),1.39(sextet,J=7.4Hz,2H),0.92(t,J=7.4Hz,3H). Under an argon atmosphere, 50 mL of 1 M boron tribromide dichloromethane solution (50.0 mmol) was slowly added dropwise to 99 mL of a dichloromethane solution (3.48 g, 10.0 mmol) of 2-chloro-4,4'-dimethoxy-N-butylbenzanilide under ice cooling. After addition, the temperature was raised to room temperature and the mixture was stirred for 22 hours. After the reaction was complete, the mixture was cooled on ice, and the reaction solution was heated to room temperature with ice water added and stirred for 20 minutes. After concentrating the solvent under reduced pressure, the precipitated solid was collected by filtration, washed with water, and vacuum dried. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 5:95) and reprecipitation with ethyl acetate / hexane to obtain a white solid of N-butyl-2-chloro-4,4'-dihydroxybenzanilide (compound 4) (yield: 2.57 g, yield: 80%). 1H-NMR(400MHz,DMSO-d6):δ9.90(brs,1H),9.54(brs,1H),6.97(d,J=8.4Hz,1H),6.93(d,J=8.7Hz,2H),6.61(d,J=2.2Hz,1H),6.5 7(d,J=8.7Hz,2H),6.50(dd,J=8.4,2.2Hz,1H),3.72(t,J=7.2Hz,2H),1.49-1.42(m,2H),1.37-1.28(m,2H),0.88(t,J=7.2Hz,3H). [Monomer Example 5]

[0179] [ka]

[0180] Under an argon atmosphere, 21 mL of a DMF solution (3.00 g, 10.3 mmol) of 2-chloro-4,4'-dimethoxy-benzanilide was added to a solution (21 mL) of DMF. Under ice cooling, 55% sodium hydride (0.76 g, 17.5 mmol) and 1-iodooctane (2.78 mL, 15.4 mmol) were added, and the mixture was heated to room temperature and stirred for 4 hours. After the reaction was complete, the mixture was cooled on ice, and 120 mL of aqueous ammonium chloride solution was added to the reaction mixture. The mixture was extracted with ethyl acetate (50 mL x 2), and the organic layer was washed with water (30 mL x 2) and saturated brine (20 mL x 5). The mixture was then dried over anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 3:1) to quantitatively obtain 4.15 g of the yellow viscous substance (2-chloro-4,4'-dimethoxy-N-octylbenzanilide). 1 H-NMR (400MHz, CDCl3): δ7.01(d,J=8.9Hz,2H),6.97(d,J=8.5Hz,1H),6.71(d,J=2.4Hz,1H),6.69(d,J=8.9Hz,2H),6.57(dd ,J=8.5,2.4Hz,1H),3.87-3.83(m,2H),3.73(s,3H),3.70(s,3H),1.63-1.56(m,2H),1.37-1.26(m,10H),0.89-0.85(m,3H). Under an argon atmosphere, 49 mL of 1 M boron tribromide dichloromethane solution (49.0 mmol) was slowly added dropwise to 97 mL of a dichloromethane solution (3.95 g, 9.78 mmol) of 2-chloro-4,4'-dimethoxy-N-octylbenzanilide under ice cooling. After addition, the temperature was raised to room temperature and the mixture was stirred for 24 hours. After the reaction was complete, the mixture was cooled on ice, and the reaction solution was heated to room temperature and stirred for 20 minutes. After concentrating the solvent under reduced pressure, the precipitated solid was collected by filtration, washed with water, and vacuum dried. The crude product was purified by silica gel column chromatography (hexane:ethyl acetate = 5:95) to obtain a white solid of 2-chloro-4,4'-dihydroxy-N-octylbenzanilide (compound 5) (yield: 3.30 g, yield: 90%). 1 H-NMR(400MHz,DMSO-d6):δ9.61(brs,2H),6.96(d,J=8.4Hz,1H),6.93(d,J=8.7Hz,2H),6.61(d,J=2.2Hz,1H),6.56(d, J=8.7Hz,2H),6.50(dd,J=8.4,2.2Hz,1H),3.73-3.69(m,2H),1.50-1.43(m,2H),1.28-1.24(m,10H),0.87-0.83(m,3H). [Monomer Example 6]

[0181] [ka]

[0182] Under an argon atmosphere, thionyl chloride (6.16 mL, 85.1 mol) and DMF (90 μL) were added to a toluene solution (9 mL) of 2,5-dichloroterephthalic acid (2.00 g, 8.51 mmol), and the mixture was heated under reflux for 2 hours. After the reaction was complete, the solvent was concentrated under reduced pressure, and the solvent was further removed by azeotropic distillation with THF. After vacuum drying, the mixture was purged with argon, and the resulting acid chloride was prepared in a THF (15 mL) solution.

[0183] A solution of 4-(methylamino)phenol sulfate (2.93 g, 8.51 mmol) in THF (15 mL) - water (15 mL) was cooled to 0°C, and sodium bicarbonate (3.58 g, 42.6 mmol) was added while stirring. Then, the THF solution of the acid chloride prepared above was rapidly added dropwise. The mixture was heated to room temperature and vigorously stirred for 15 hours, after which it was concentrated under reduced pressure. After filtering the solid formed in the system, it was washed with water (200 mL) and reprecipitation with hexane (50 mL) - ethyl acetate (50 mL) to obtain a light brown solid of 2,5-dichloro-N,N'-bis(hydroxyphenyl)-N,N'-dimethyl-1,4-benzenedicaramide (compound 6) (yield: 1.85 g, yield: 49%). This compound was used in the next reaction without further purification. 1 H-NMR (400MHz, DMSO-d6): δ9.55(brs,2H),7.29(s,2H),6.96(d,J=8.7Hz,4H),6.57(d,J=8.7hz,4H),3.24(s,6H). [Monomer Example 7]

[0184] [ka]

[0185] Under an argon atmosphere, thionyl chloride (19.5 mL) and DMF (250 μL) were added to a solution of 2-chloro-4-methoxybenzoic acid (5.00 g, 26.8 mmol) in toluene (25 mL), and the mixture was stirred at 100 °C for 1 hour. After that, the thionyl chloride was removed under reduced pressure, and THF (45 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0186] A solution of 4-amino-1-naphthol hydrochloride (5.24 g, 26.8 mmol) in THF (45 mL) and water (45 mL) was cooled to 0°C. Sodium bicarbonate (5.63 g, 67.0 mmol) was added while stirring, and then the previously prepared acid chloride THF solution was added dropwise over 5 minutes. The mixture was heated to room temperature, stirred vigorously overnight, and then concentrated under reduced pressure. The solid formed in the system was filtered off and washed with water (200 mL) to obtain a crude solid. This was further reprecipitated in a mixed solvent of hexane (50 mL), ethyl acetate (10 mL), and ethanol (5 mL) to obtain a brown solid of 2-chloro-N-(4-hydroxy-1-naphthalenyl)-4-methoxybenzamide (yield: 4.82 g, yield: 55%). 1 H-NMR(400MHz,DMSO-d6):δ10.3-10.2(brs,1H),10.1(s,1H),8.17(d,J=8.0Hz,1H),7.99(d,J=8.2Hz,1H),7.66(d,J=8.5Hz,1H ),7.57-7.44(m,2H),7.38(d,J=8.0,1H),7.16(d,J=2.4Hz,1H),7.05(dd,J=8.5,2.5Hz,1H),6.88(d,J=8.0Hz,1H),3.85(s,3H). Under an argon atmosphere, a solution of 2-chloro-N-(4-hydroxy-1-naphthalenyl)-4-methylbenzamide (3.50 g, 10.7 mmol) in DMF (50 mL) was cooled on ice, then 55% sodium hydride (1.17 g, 26.8 mmol) was added and the mixture was stirred for 10 minutes, followed by the addition of iodomethane (3.19 g, 22.5 mmol). The reaction system was stirred for 15 hours while being heated to room temperature, then cooled again on ice and saturated ammonium chloride aqueous solution (100 mL) was added. The mixture was extracted with ethyl acetate (100 mL x 3) and dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure, and the resulting solid was reprecipitation in a mixed solvent of hexane (100 mL), ethyl acetate (5 mL), and ethanol (1 mL) to obtain a brown solid of 2-chloro-4-methoxy-N-(4-methoxy-1-naphthalenyl)-N-methylbenzamide (yield: 2.91 g, yield: 83%). 1H-NMR (400MHz, CDCl3): δ7.90(m,1H),7.91(m,1H),7.62(m,1H),7.50(m,1H),7.32(m,1H), 6.86(m,1H),6.69(m,1H),6.59(m,1H),6.29(m,1H),3.93(s,3H),3.61(s,3H),3.51(s,3H). Under an argon atmosphere, a suspension of 2-chloro-4-methoxy-N-(4-methoxy-1-naphthalenyl)-N-methylbenzamide (2.90 g, 8.15 mmol) in dichloromethane (80 mL) was cooled to 0°C, and then 1 M boron tribromide dichloromethane solution (32.6 mL, 32.6 mmol) was added dropwise over 15 minutes. The reaction system was raised to room temperature, stirred for 16 hours, and then cooled again to 0°C. After adding ice (100 g), the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure, and the resulting solid was filtered off. Purification by silica gel chromatography (hexane:ethyl acetate = 5:95) yielded a light brown solid of 2-chloro-4-hydroxy-N-(4-hydroxy-1-naphthalenyl)-N-methylbenzamide (compound 7) (yield: 2.65 g, yield: 99%). 1 H-NMR (400MHz, DMSO-d6): δ10.6-9.63(br,2H),8.07(m,1H),7.85(m,1H),7.59(m,1H),7. 46(m,1H),7.26(m,1H),6.87(m,1H),6.67(m,1H),6.55(m,1H),6.25(m,1H),3.34(s,3H). [Monomer Example 8]

[0187] [ka]

[0188] Under an argon atmosphere, paraformaldehyde (2.30 g, 79.0 mmol) was added to a methanol (23 mL) solution of 5-methoxy-2-aminopyridine (0.98 g, 7.90 mmol), and 5M sodium methoxide methanol solution (7.66 mL, 39.5 mmol) was added dropwise. The mixture was stirred overnight and then cooled to 0°C. Sodium borohydride (0.90 g, 23.7 mmol) was added, and the mixture was stirred at room temperature for 4 hours. After extraction with ethyl acetate (50 mL x 3), the mixture was dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure to obtain a brown oily substance of N-methyl-5-methoxy-2-aminopyridine (yield: 0.97 g, yield: 89%). 1 H-NMR (400MHz, CDCl3): δ7.84(d,J=2.7Hz,1H),7.13(dd,J=8.8,3.0Hz,1H),6 .38(dd,J=8.9,0.5Hz,1H),4.24(brs,1H),3.78(s,3H),2.89(d,J=4.5Hz,3H). Under an argon atmosphere, thionyl chloride (8.2 mL) and DMF (150 μL) were added to a toluene (10 mL) solution of 2-chloro-4-methoxybenzoic acid (2.12 g, 11.4 mmol), and the mixture was stirred at 100 °C for 1 hour. The thionyl chloride was then removed by distillation under reduced pressure. Pyridine (10 mL) was added to the resulting residue and the mixture was cooled to 0 °C. A pyridine (5 mL) solution of N-methyl-5-methoxy-2-aminopyridine (1.05 g, 7.57 mmol) was added dropwise over 5 minutes. The mixture was heated to room temperature and vigorously stirred for 6 hours. After extraction with ethyl acetate (50 mL x 3), the mixture was dried over anhydrous sodium sulfate. The resulting residue was purified by silica gel chromatography (hexane:ethyl acetate = 50:50 to 30:70) to obtain a brown oily substance of 2-chloro-4-methoxy-N-(5-methoxy-2-pyridinyl)-N-methylbenzamide (yield: 1.47 g, yield: 63%). 1 H-NMR (400MHz, CDCl3): δ8.07(s,1H),7.11(brs,1H),7.02(brs,1H),6.81(brs,2H),6.66(brs,1H),3.80(s,3H),3.75(s,3H),3.47(s,3H). Under an argon atmosphere, a solution of 2-chloro-4-methoxy-N-(5-methoxy-2-pyridinyl)-N-methylbenzamide (1.20 g, 3.92 mmol) in dichloromethane (20 mL) was cooled to 0°C, and then a 1 M boron tribromide dichloromethane solution (31.3 mL, 31.3 mmol) was added dropwise over 15 minutes. The reaction system was raised to room temperature, stirred for 24 hours, and then cooled again to 0°C. After adding ice (100 g), the mixture was stirred at room temperature until the ice dissolved. The mixture was extracted with ethyl acetate (50 mL x 3) and then dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel chromatography (hexane:ethyl acetate = 5:95) to obtain a white solid of 2-chloro-4-hydroxy-N-(5-hydroxy-2-pyridinyl)-N-methylbenzamide (compound 8) (yield: 0.68 g, yield: 62%). 1 H-NMR (400MHz, DMSO-d6): δ10.04(brs,2H),7.87(d,J=2.5Hz,1H),7.02(brs,2H),6.90(brs,1H),6.70(s,1H),6.60(d,J=6.5Hz,1H),3.29(s,3H). [Monomer Example 9]

[0189] [ka]

[0190] Under an argon atmosphere, tri-tert-butylphosphine tetrafluoroborate (0.026 g, 0.09 mmol) and bis(dibenzylideneacetone) (0.052 g, 0.09 mmol) were added to a toluene (5 mL) solution of 2-bromo-6-methoxynaphthalene (1.07 g, 4.51 mmol), and then 1 M lithium bis(trimethylsilyl)amide toluene solution (5.00 mL, 5.00 mmol) was added dropwise. After stirring the mixture overnight, the pH was adjusted to 3 with 2 M hydrochloric acid. The solid formed in the system was filtered off, dissolved in 2 M sodium hydroxide aqueous solution (20 mL), extracted with dichloromethane (20 mL x 3), and dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure to obtain a brown solid of 2-bromo-6-methoxynaphthalene (yield: 0.67 g, yield: 85%). 1 H-NMR (400MHz, CDCl3): δ7.56(d,J=8.7Hz,1H),7.51(d,J=8.6Hz,1H),7.08-7.04(m,2H),6.97-6.93(m,2H),3.88(s,3H),3.73(brs,2H). Under an argon atmosphere, 10 mL of toluene was used to a solution of 2-chloro-4-methoxybenzoic acid (1.80 g, 10.7 mmol). 6.0 mL of thionyl chloride and 150 μL of DMF were added, and the mixture was stirred at 100°C for 1 hour. The thionyl chloride was then removed under reduced pressure, and 14 mL of THF was added to the resulting residue. This entire solution was used in the next reaction.

[0191] A solution of 2-amino-6-methoxynaphthalene (1.68 g, 9.70 mmol) in THF (14 mL) and water (14 mL) was cooled to 0°C. Sodium bicarbonate (2.04 g, 24.3 mmol) was added while stirring, and then the previously prepared acid chloride THF solution was added dropwise over 5 minutes. The mixture was heated to room temperature and vigorously stirred for 4 hours, after which it was concentrated under reduced pressure. After filtering out the solid formed in the system, it was washed with water (50 mL) and hexane:ethyl acetate (75:25) (50 mL) to obtain a light brown solid of 2-chloro-4-methoxy-N-(6-methoxy-2-naphthalenyl)benzamide (yield: 3.04 g, yield: 92%). 1H-NMR (400MHz, CDCl3): δ8.26(d,J=1.3Hz,1H),8.20(s,1H),7.87(d,J=8.6Hz,1H),7.73(d,J=8.8Hz,2H),7.55(dd,J=9.0,2.0Hz, 1H),7.16(dd,J=9.0,2.6Hz,1H),7.11(d,J=2.5,1H),6.98(d,J=2.5Hz,1H),6.93(dd,J=8.8,2.5Hz,1H),3.92(s,3H),3.87(s,3H). Under an argon atmosphere, a solution of 2-chloro-4-methoxy-N-(6-methoxy-2-naphthalenyl)benzamide (2.98 g, 8.73 mmol) in DMF (24 mL) was cooled on ice, then 55% sodium hydride (1.14 g, 26.2 mmol) was added and the mixture was stirred for 30 minutes. Finally, a solution of iodomethane (0.82 mL, 13.1 mmol) in DMF (12 mL) was added. The reaction system was stirred for 4 hours while raising the temperature to room temperature. The mixture was extracted with ethyl acetate (100 mL x 3) and then dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel chromatography (hexane:ethyl acetate = 60:40~40:60) to obtain a light brown oily substance of 2-chloro-4-methoxy-N-(6-methoxy-2-naphthalenyl)-N-methylbenzamide (yield: 2.82 g, yield: 91%). 1 H-NMR (400MHz, CDCl3): δ7.57(dd,J=16.7,8.8Hz,2H),7.49(s,1H),7.17(d,J=8.7Hz,1H),7.11(dd,J=8.7,2.0Hz, 1H),7.07(d,J=8.6Hz,1H),7.03(s,1H),6.67(s,1H),6.52(d,J=8.1Hz,1H),3.88(s,3H),3.64(s,3H),3.55(s,3H). Under an argon atmosphere, a solution of 2-chloro-4-methoxy-N-(6-methoxy-2-naphthalenyl)-N-methylbenzamide (1.15 g, 5.23 mmol) in dichloromethane (32 mL) was cooled to 0°C, and then a 1 M boron tribromide dichloromethane solution (13.0 mL, 13.0 mmol) was added dropwise over 15 minutes. The reaction system was raised to room temperature, stirred for 16 hours, and then cooled again to 0°C. After adding ice (100 g), the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure, and the resulting solid was filtered to obtain a white solid of 2-chloro-4-hydroxy-N-(6-hydroxy-2-naphthalenyl)-N-methylbenzamide (compound 9) (yield: 1.04 g, yield: 98%). 1 H-NMR(400MHz,MeOD):δ7.57(d,J=8.8Hz,1H),7.54(s,1H),7.49(d,J=8.7Hz,1H),7.17(d d,J=8.8,1.7Hz,1H),7.05-7.01(m,3H),6.59(s,1H),6.47(d,J=8.9Hz,1H),3.50(s,3H). [Monomer Example 10]

[0192] [ka]

[0193] Under an argon atmosphere, thionyl chloride (3.5 mL) and DMF (100 μL) were added to a solution of 2-chloro-4-methoxybenzoic acid (1.08 g, 5.54 mmol) in toluene (5 mL), and the mixture was stirred at 100 °C for 1 hour. After removing the thionyl chloride under reduced pressure, THF (8 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0194] A solution of 4-(4-methoxyphenyl)aniline (1.00 g, 5.04 mmol) in THF (8 mL) and water (8 mL) was cooled to 0°C. Sodium bicarbonate (1.05 g, 12.6 mmol) was added while stirring, and then the previously prepared acid chloride THF solution was added dropwise over 5 minutes. The mixture was heated to room temperature and vigorously stirred for 4 hours, after which it was concentrated under reduced pressure. After filtering out the solid formed in the system, it was washed with water (50 mL) and hexane:ethyl acetate (75:25) (50 mL) to obtain a light brown solid of 2-chloro-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)benzamide (yield: 1.68 g, yield: 91%). 1 H-NMR (400MHz, CDCl3): δ8.10(s,1H),7.85(d,J=8.7Hz,1H),7.70(d,J=8.4Hz,2H),7.56(d,J=8.8H z,2H),7.54-7.52(m,2H),6.99-6.97(m,3H),6.92(dd,J=8.6,2.5Hz,1H),3.87(s,3H),3.86(s,3H). Under an argon atmosphere, a solution of 2-chloro-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)benzamide (0.96 g, 2.61 mmol) in DMF (7 mL) was cooled on ice. Then, 55% sodium hydride (0.34 g, 7.84 mmol) was added and the mixture was stirred for 30 minutes. Finally, a solution of iodomethane (0.24 mL, 3.92 mmol) in DMF (3.5 mL) was added. The reaction system was stirred for 6 hours while gradually increasing the temperature to room temperature. The mixture was extracted with ethyl acetate (50 mL x 3) and then dried over anhydrous sodium sulfate. The obtained organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel chromatography (hexane:ethyl acetate = 60:40 to 40:60) to obtain a light brown oily substance of 2-chloro-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (yield: 2.82 g, yield: 91%). 1H-NMR (400MHz, CDCl3): δ7.45(d,J=8.1Hz,2H),7.38(d,J=7.3Hz,2H),7.12-7.06(m,3H),6.9 4(d,J=8.6Hz,2H),6.74(s,1H),6.60(d,J=7.1Hz,1H),3.84(s,3H),3.71(s,3H),3.51(s,3H). Under an argon atmosphere, a solution of 2-chloro-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (1.88 g, 4.93 mmol) in dichloromethane (49 mL) was cooled to 0°C, and then a 1 M boron tribromide dichloromethane solution (20 mL, 20.0 mmol) was added dropwise over 15 minutes. The reaction system was raised to room temperature, stirred for 16 hours, and then cooled again to 0°C. After adding ice (100 g), the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure, and the resulting solid was filtered to obtain a white solid of 2-chloro-4-hydroxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (compound 10) (yield: 1.65 g, yield: 95%). 1 H-NMR(400MHz,MeOD):δ7.39(dd,J=17.3,7.9Hz,4H),7.19(d,J=7.3Hz,2H),7.05(d, J=8.7Hz,1H),6.81(d,J=8.3Hz,2H),6.66(s,1H),6.54(d,J=8.1Hz,1H),3.46(s,3H). [Monomer Example 11]

[0195] [ka]

[0196] Under an argon atmosphere, 2-chloro-4-methoxybenzoic acid (5.98 g, 32.0 mmol) was dissolved in toluene (30 mL), to which thionyl chloride (20.0 mL) and DMF (2 drops) were added. After heating under reflux for 1 hour, the thionyl chloride and solvent were removed under reduced pressure, and THF (90 mL) was added to the resulting residue. This entire solution was used in the following reaction.

[0197] To a solution of 5-amino-2-naphthol (5.00 g, 31.4 mmol) in THF (100 mL), DIPEA (6.5 mL, 38.2 mmol) and the previously prepared acid chloride solution in THF were slowly added dropwise. This mixture was vigorously stirred at room temperature for 48 hours. After the reaction was complete, the mixture was concentrated under reduced pressure, and then ethyl acetate (100 mL) and water (200 mL) were added. After separating the organic layer, it was extracted with ethyl acetate (100 mL x 2). The combined organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The crude product obtained was filtered with ethyl acetate (10 mL) / ethanol (5 mL) / hexane to obtain a white solid of 2-chloro-N-(6-hydroxy-1-naphthalenyl)-4-methoxybenzamide (yield: 9.27 g, yield: 88%). 1 H-NMR (400MHz, DMSO-d6): δ10.29(s,1H),9.80(s,1H),7.99(m,1H),7.70-7.56(m,2H),7.51-7.36(m,2H),7.20-6.98(m,4H),3.85(s,3H). Under an argon atmosphere, a solution of 2-chloro-N-(6-hydroxy-1-naphthalenyl)-4-methoxybenzamide (3.28 g, 10.0 mmol) in DMF (50 mL) was cooled on ice. Then, 55% sodium hydride (1.09 g, 25.0 mmol) was added and the mixture was stirred for 10 minutes. Iodomethane (1.31 mL, 21.0 mmol) was added, and the mixture was stirred for 15 hours while increasing the temperature to room temperature. After the reaction was complete, the mixture was cooled again on ice, saturated ammonium chloride aqueous solution (100 mL) was added, and the mixture was extracted with ethyl acetate (100 mL x 3). The combined organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain a white solid of 2-chloro-4-methoxy-N-(6-methoxy-1-naphthalenyl)-N-methylbenzamide (yield: 2.39 g, yield: 67%). 1 H-NMR (400MHz, CDCl3): δ7.89(m,1H),7.56(m,1H),7.38-7.20(m,3H),7.10(m,1 H),6.86(m,1H)6.69(m,1H),6.29(m,1H),3.92(s,3H),3.60(s,3H),3.53(s,3H). Under an argon atmosphere, a suspension of 2-chloro-4-methoxy-N-(6-methoxy-1-naphthalenyl)-N-methylbenzamide (2.31 g, 6.49 mmol) in dichloromethane (65 mL) was cooled to 0°C. Then, a 1 M boron tribromide dichloromethane solution (26.0 mL, 26.0 mmol) was added dropwise over 15 minutes, and the mixture was heated to room temperature and stirred for 15 hours. After the reaction was complete, the mixture was cooled again to 0°C, ice (100 g) was added, and the mixture was stirred at room temperature. The resulting solid was filtered and dried under reduced pressure to obtain a white solid of 2-chloro-4-hydroxy-N-(6-hydroxy-1-naphthalenyl)-N-methylbenzamide (compound 11) (yield: 2.06 g, yield: 97%). 1 H-NMR (400MHz, DMSO-d6): δ9.93-9.83(m,2H),7.84(m,1H),7.54(m,1H),7.31-7.06(m,4H),6.89(m,1H),6.56(m,1H),6.27(m,1H),3.36(s,3H). [Monomer Example 12]

[0198] [ka]

[0199] Under an argon atmosphere, thionyl chloride (16.0 mL) and DMF (250 μL) were added to a solution of 2-bromo-4-methoxybenzoic acid (5.00 g, 21.6 mmol) in toluene (25 mL), and the mixture was stirred at 100 °C for 1 hour. After that, the thionyl chloride was removed under reduced pressure, and THF (45 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0200] A solution of 4-(aminomethyl)phenol sulfate (3.72 g, 10.8 mmol) in THF (45 mL)-water (45 mL) was cooled to 0°C, and sodium bicarbonate (4.54 g, 54.0 mmol) was added while stirring. Then, the previously prepared acid chloride THF solution was added dropwise over 5 minutes. The mixture was heated to room temperature, stirred vigorously for 4 hours, and then concentrated under reduced pressure. The mixture was extracted with ethyl acetate (100 mL x 3) and dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure to obtain a brown solid of 2-bromo-4-methoxy-N-(4-hydroxyphenyl)-N-methylbenzamide (yield: 6.77 g, yield: 93%). 1 H-NMR(400MHz,DMSO-d6):δ9.49(brs,1H),7.14(d,J=8.5Hz,1H),7.03-7.00(m,3 H),6.76(dd,J=8.5,2.7Hz,1H),6.57(d,J=8.8Hz,2H),3.69(s,3H),3.28(s,3H). Under an argon atmosphere, a suspension of 2-bromo-4-methoxy-4'-hydroxy-N-methylbenzamide (3.36 g, 10.0 mmol) in dichloromethane (100 mL) was cooled to 0°C, and then 1 M boron tribromide dichloromethane solution (20.0 mL, 20.0 mmol) was added dropwise over 15 minutes. The reaction system was raised to room temperature, stirred for 16 hours, and then cooled again to 0°C. After adding ice (150 g), the mixture was stirred at room temperature until the ice dissolved. The mixture was extracted with ethyl acetate (100 mL x 3) and then dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel chromatography (chloroform:methanol = 95:5~90:10) to obtain a white solid of 2-bromo-4-hydroxy-N-(4-hydroxyphenyl)-N-methylbenzamide (compound 12) (yield: 2.47 g, yield: 77%). 1 H-NMR (400MHz, DMSO-d6): δ9.95(brs,1H),9.51(brs,1H),7.01-6.97(m,3H),6.78(d,J=1.7Hz,1H),6.57-6.55(m,3H),3.26(s,3H). [Monomer Example 13]

[0201] [ka]

[0202] Under an argon atmosphere, thionyl chloride (6 mL) and DMF (150 μL) were added to a solution of 2-bromo-4-methoxybenzoic acid (1.92 g, 8.31 mmol) in toluene (10 mL), and the mixture was stirred at 100 °C for 1 hour. After that, the thionyl chloride was removed under reduced pressure, and THF (15 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0203] A solution of 4-(4-methoxyphenyl)aniline (1.50 g, 7.55 mmol) in THF (15 mL) and water (15 mL) was cooled to 0°C. Sodium bicarbonate (1.59 g, 18.9 mmol) was added while stirring, and then the previously prepared acid chloride THF solution was added dropwise over 5 minutes. The mixture was heated to room temperature and vigorously stirred for 4 hours, after which it was concentrated under reduced pressure. After filtering out the solid formed in the system, it was washed with water (50 mL) and ethyl acetate (50 mL) to obtain a light brown solid of 2-bromo-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)benzamide (yield: 2.57 g, yield: 82%). 1 H-NMR (400MHz, CDCl3): δ7.84(s,1H),7.72-7.68(m,3H),7.56(d,J=8.4Hz,2 H),7.54-7.50(m,2H),7.16(d,J=2.4Hz,1H),6.99-6.93(m,3H),3.86(s,6H). Under an argon atmosphere, a solution of 2-bromo-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)benzamide (2.51 g, 6.08 mmol) in DMF (18 mL) was cooled on ice. Then, 55% sodium hydride (0.80 g, 18.3 mmol) was added and the mixture was stirred for 30 minutes. Finally, a solution of iodomethane (0.57 mL, 9.13 mmol) in DMF (7 mL) was added. The reaction system was stirred for 6 hours while gradually increasing the temperature to room temperature. The mixture was extracted with ethyl acetate (100 mL x 3) and then dried over anhydrous sodium sulfate. The obtained organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel chromatography (hexane:ethyl acetate = 60:40 to 40:60) to obtain a light brown oily substance of 2-bromo-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (yield: 2.46 g, yield: 95%). 1 H-NMR (400MHz, CDCl3): δ7.44(d,J=7.9Hz,2H),7.37(d,J=7.2Hz,2H),7.14(d,J=6.9Hz,2H),7.03(d ,J=8.2Hz,1H),6.94(d,J=7.4Hz,3H),6.63(d,J=7.4Hz,1H),3.83(s,3H),3.70(s,3H),3.51(s,3H). Under an argon atmosphere, a solution of 2-bromo-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (2.46 g, 5.78 mmol) in dichloromethane (58 mL) was cooled to 0°C, and then a 1 M boron tribromide dichloromethane solution (23 mL, 23.0 mmol) was added dropwise over 15 minutes. The reaction system was raised to room temperature, stirred for 16 hours, and then cooled again to 0°C. After adding ice (100 g), the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure, and the resulting solid was filtered to obtain a white solid of 2-bromo-4-hydroxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (compound 13) (yield: 2.12 g, yield: 92%). 1H-NMR(400MHz,MeOD):δ7.39(dd,J=17.6,8.1Hz,4H),7.22(d,J=8.0Hz,2H),7.03(d, J=8.0Hz,1H),6.86(s,1H),6.81(d,J=8.2Hz,2H),6.58(d,J=8.2Hz,1H),3.46(s,3H). [Monomer Example 14]

[0204] [ka]

[0205] Under an argon atmosphere, a 90 mL solution of methyl 4-methoxysalicylate (5.40 g, 30.0 mmol) in dichloromethane was cooled to 0°C, and diisopropylethylamine (6.12 mL, 36.0 mmol) was added and the mixture was stirred for 10 minutes. Then, trifluoromethanesulfonic anhydride (6.39 mL, 39.0 mmol) was added dropwise, and the reaction temperature was raised to room temperature and stirred for 12 hours. After the reaction was complete, the mixture was washed with saturated sodium bicarbonate aqueous solution and water, and the aqueous layer was re-extracted with dichloromethane. The combined organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 94:6) to obtain a brown oily substance of methyl 4-methoxy-2-trifluoromethanesulfonyloxybenzoate (yield: 6.59 g, yield: 70%). 1 H-NMR (400MHz, CDCl3): δ8.05(d,1H,J=8.8Hz),6.95(m,1H),6.77(m,1H),3.93(s,3H),3.88(s,3H). 19 F-NMR (376MHz, CDCl3): δ-73.2(s). 30 mL of a dioxane solution (1.80 g, 5.70 mmol) of methyl 4-methoxy-2-trifluoromethanesulfonyloxybenzoate was mixed with 30 mL of 6 M hydrochloric acid and stirred at 100°C for 24 hours. After the reaction was complete, the reaction mixture was concentrated and extracted with ethyl acetate. The organic layer was then extracted with saturated sodium bicarbonate aqueous solution, and the aqueous layer was acidified with 2 M hydrochloric acid. The aqueous layer was again extracted with ethyl acetate, and the combined organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a white solid of 4-methoxy-2-trifluoromethanesulfonyloxybenzoic acid (yield: 1.36 g, yield: 79%). 1 H-NMR (400MHz, DMSO-d6): δ13.50(bs,1H),8.03(m,1H),7.18(m,1H),7.01(m,1H),3.88(s,3H). 19 F-NMR (376MHz, DMSO-d6): δ-73.4(s). Under an argon atmosphere, thionyl chloride (4.10 mL, 56.6 mmol) and DMF (50 μL) were added to a solution of 4-methoxy-2-trifluoromethanesulfonyloxybenzoic acid (1.70 g, 5.66 mmol) in toluene (10 mL), and the mixture was stirred at 100 °C for 1 hour. After the reaction was complete, thionyl chloride was removed under reduced pressure, and dichloromethane (10 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0206] Under an argon atmosphere, triethylamine (1.57 g, 11.3 mmol) was added to a solution of N-methyl-p-anisidine (0.78 g, 5.66 mmol) in dichloromethane (10 mL) and cooled to 0°C. The previously prepared dichloromethane solution of acid chloride was added dropwise over 5 minutes. The mixture was heated to room temperature and stirred for 3 hours. Water was added to the resulting mixture, and it was extracted with dichloromethane. The organic layer was washed with saturated sodium bicarbonate aqueous solution, 2 M hydrochloric acid, and water, and then dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure to obtain an orange solid of 2-trifluoromethanesulfonyloxy-4,4'-dimethoxy-N-methylbenzanilide (yield: 1.94 g, yield: 82%). 1H-NMR (400MHz, CDCl3): δ7.28(m,1H), 6.98-6.95(m,2H), 6.75-6.73(m,2H), 6.754(m,1H), 6.58(m,1H), 3.76(s,3H), 3.74(s,3H), 3.43(s,3H). 19 F-NMR (376MHz, CDCl3): δ-73.5(s). Under an argon atmosphere, a suspension of 2-trifluoromethanesulfonyloxy-4,4'-dimethoxy-N-methylbenzanilide (2.00 g, 4.77 mmol) in dichloromethane (25 mL) was cooled to 0°C, and then 19.1 mL, 19.1 mmol, 1 M boron tribromide dichloromethane solution was added dropwise, and the mixture was stirred for 1 hour. The reaction system was then heated to room temperature and stirred for 24 hours. Ethyl acetate (100 mL) and saturated sodium bicarbonate aqueous solution (100 mL) were added to a 300 mL flask and cooled to 0°C. The reaction mixture was then added dropwise and stirred for 10 minutes. The aqueous layer was extracted twice with ethyl acetate, and the combined organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 5:95). Furthermore, the obtained solid was reprecipitated with DMF (4 mL)-water (100 mL) to obtain a white solid of 2-trifluoromethanesulfonyloxy-4',4-dihydroxy-N-methylbenzanilide (compound 14) (yield: 1.19 g, yield: 64%). 1 H-NMR (400MHz, DMSO-d6): δ10.50(brs,1H),9.50(s,1H),7.18(m,1H),6.89-6.88(m,2H),6.69(m,1H),6.60(m,1H),6.61-6.59(m,2H),3.26(s,3H). 19 F-NMR (376MHz, DMSO-d6): δ-73.8(s). [Monomer Example 15]

[0207] [ka]

[0208] Under an argon atmosphere, 10 mL of 2M potassium carbonate aqueous solution was added to a solution of 4-bromo-N-methylaniline (1.87 g, 10.0 mmol), a dichloromethane complex of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (205 mg, 251 μmol), and 4-methoxyphenylboronic acid (2.29 g, 15.1 mmol) in 1,4-dioxane (40 mL). After stirring at 100 °C for 10 hours, the solid formed in the system was removed by Celite filtration, and the filtrate was extracted with ethyl acetate (100 mL x 3) and dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (hexane:chloroform = 30:70~20:80) to obtain a white solid of 4'-methoxy-N-methyl-(1,1'-biphenyl)-4-amine (yield: 1.37 g, yield: 64%). 1 H-NMR (400MHz, CDCl3): δ7.48-7.44(m,2H),7.42-7.38(m,2H),6.96-6.92(m,2H),6.69-6.66(m,2H),3.84(s,3H),3.75(brs,1H),2.88(s,3H). Under an argon atmosphere, thionyl chloride (5 mL) and DMF (100 μL) were added to a solution of 2-trifluoromethanesulfonyloxy-4-methoxybenzoic acid (2.12 g, 7.05 mmol) in toluene (12 mL). After stirring at 100 °C for 1 hour, the thionyl chloride was removed under reduced pressure, and dichloromethane (12 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0209] A solution of 4'-methoxy-N-methyl-(1,1'-biphenyl)-4-amine (1.37 g, 6.41 mmol) in dichloromethane (12 mL) was cooled to 0°C, and triethylamine (1.79 mL, 12.8 mmol) was added while stirring. Then, the previously prepared dichloromethane solution of acid chloride was added dropwise over 5 minutes. The mixture was heated to room temperature and vigorously stirred for 4 hours. The mixture was concentrated under reduced pressure, extracted with ethyl acetate (100 mL x 3), and dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (hexane:ethyl acetate = 70:30~60:40) to obtain a light brown oily substance of 2-trifluoromethanesulfonyloxy-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (yield: 2.75 g, yield: 87%). 1 H-NMR (400MHz, CDCl3): δ7.48-7.45(m,2H),7.41(d,J=7.9Hz,2H),7.35(d,J=9.1Hz,1H),7.09(s, 2H),6.97-6.93(m,2H),6.77(d,J=8.5Hz,1H),6.60(s,1H),3.84(s,3H),3.77(s,3H),3.50(s,3H). 19 F-NMR(376MHz, CDCl3):δ-73.46(s). Under an argon atmosphere, a solution of 2-trifluoromethanesulfonyloxy-4-methoxy-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (2.75 g, 5.55 mmol) in dichloromethane (56 mL) was cooled to 0°C, and then a 1 M boron tribromide dichloromethane solution (23 mL, 23.0 mmol) was added dropwise over 15 minutes. The reaction system was raised to room temperature, stirred for 16 hours, and then cooled again to 0°C. After adding ice (100 g), the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure, extracted with ethyl acetate (100 mL x 3), and then dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (hexane:ethyl acetate = 25:75~15:85) to obtain a white solid of 2-trifluoromethanesulfonyloxy-4-hydroxy-N-(4'-hydroxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (compound 15) (yield: 2.57 g, yield: 99%). 1 H-NMR(400MHz,MeOD):δ7.46(d,J=7.8Hz,2H),7.42-7.39(m,2H),7.30(d,J=8.1Hz,1H),7 .16(d,J=5.9Hz,2H),6.84-6.80(m,2H),6.73(d,J=5.4Hz,1H),6.56(s,1H),3.45(s,3H). 19 F-NMR(376MHz,MeOD):δ-75.54(s). [Monomer Example 16]

[0210] [ka]

[0211] Under an argon atmosphere, 4-bromo-2-chlorobenzoic acid (4.00 g, 17.0 mmol) was dissolved in toluene (30 mL), to which thionyl chloride (12.4 mL, 169.8 mmol) and DMF (50 μL) were added, and the mixture was stirred at 100 °C for 1 hour. Then, thionyl chloride was removed under reduced pressure, and dichloromethane (30 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0212] Under an argon atmosphere, triethylamine (7.06 mL, 50.94 mmol) was added to a solution of 4-(methylamino)phenol sulfate (2.92 g, 8.49 mmol) in dichloromethane (30 mL), and the mixture was stirred for 5 minutes, then cooled to 0°C. The previously prepared dichloromethane solution of acid chloride was added dropwise over 5 minutes, and the mixture was heated to room temperature and stirred for 4 hours. Water was added to the resulting mixture, and it was extracted with dichloromethane. The organic layer was washed with saturated sodium bicarbonate aqueous solution, 2 M hydrochloric acid, and water, and then dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 75:25) to obtain an orange solid of 4-bromo-2-chloro-2'-hydroxy-N-methylbenzanilide (yield: 3.47 g, yield: 60%). 1 H-NMR (400MHz, CDCl3): δ7.35(d,J=1.9Hz,1H),7.19(m,1H),6.97-6.93(m,3H),6.64-6.61(m,2H),5.57(bs,1H),3.42(s,3H). Under an argon atmosphere, potassium carbonate (2.99 g, 21.6 mL), 4-methoxyphenylboronic acid (1.80 g, 11.9 mL), and tetrakistriphenylphosphine palladium (0) (0) were added to a solution of 4-bromo-2-chloro-2'-hydroxy-N-methylbenzanilide (3.7 g, 10.8 mmol) in toluene (12.5 mL) and water (12.5 mL), and the mixture was stirred at 100 °C for 12 hours. After the reaction was complete, water was added and the mixture was extracted with ethyl acetate. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 75:25) to obtain an orange solid of 2-chloro-4'-methoxy-N-(hydroxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (yield: 2.82 g, yield: 71%). 1H-NMR (400MHz, CDCl3): δ7.35(d,J=8.8Hz,2H),7.32(d,J=1.8Hz,1H),7.18(m,1H),7.08(d,J=7.7Hz,1H),6 .95(d,J=8.8Hz,2H),6.89(d,J=8.8Hz,2H),6.61(d,J=8.8Hz,2H),6.49(brs,1H),3.80(s,3H),3.42(s,3H). Under an argon atmosphere, a solution of 2-chloro-4'-methoxy-N-(hydroxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (2.5 g, 6.80 mmol) in dichloromethane (35 mL) was cooled to 0°C. Then, a 1 M boron tribromide dichloromethane solution (20.4 mL, 20.4 mmol) was added dropwise, and the reaction system was raised to room temperature and stirred for 15 hours. After the reaction was complete, the solution was cooled again to 0°C, ice (100 g) was added, and the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure to remove the dichloromethane, and the precipitated solid was filtered and washed with water. The obtained solid was dissolved in chloroform (2.0 mL) and methanol (1.0 mL), and hexane was gradually added to reprecipitation to obtain a pale yellow solid of 2-chloro-4'-hydroxy-N-(hydroxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (yield: 1.35 g, yield: 56%). 1 H-NMR (400MHz, DMSO-d6): δ9.63(brs,1H),9.60(brs,1H),7.48(m,1H),7.46(d,J=8.7Hz,2H),7.39(m, 1H),7.26(d,J=8.0Hz,1H,),7.05-7.03(m,2H),6.79(d,J=8.6Hz,2H),6.58-6.56(m,2H),3.31(s,3H). [Monomer Example 17]

[0213] [ka]

[0214] Under an argon atmosphere, potassium carbonate (1.80 g, 13.0 mL), 4-methoxyphenylboronic acid (1.09 g, 7.2 mmol), and tetrakistriphenylphosphine palladium (113 mg, 0.098 mmol) were added to a toluene (5.0 mL)-water (5.0 mL) solution of methyl 4-bromo-2-aminobenzoate (1.50 g, 6.52 mmol) and stirred at 100°C for 5 hours. After the reaction was complete, water was added and the mixture was extracted with ethyl acetate. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 90:10) to obtain a yellow solid of methyl 2-amino-4-(4-methoxyphenyl)benzoate (yield: 1.35 g, yield: 81%). 1 H-NMR (400MHz, CDCl3): δ7.88(d,J=8.3Hz,1H),7.53-7.51(m,2H),6.97-6.95(m,2H),6.86-6.82(m,2H),5.77(brs,2H),3.88(s,3H),3.84(s,3H). Under an argon atmosphere, copper(I) bromide (837 mg, 5.84 mmol), copper(II) bromide (1.30 g, 5.84 mmol), and isoamyl nitrite (0.78 mL, 5.84 mmol) were added to a 10 mL solution of methyl 2-amino-4-(4-methoxyphenyl)benzoate in acetonitrile, and the mixture was stirred at room temperature for 15 hours. After the reaction was complete, water was added, and the mixture was extracted with ethyl acetate. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 98:2) to obtain a reddish-brown oily substance of methyl 2-bromo-4-(4-methoxyphenyl)benzoate (yield: 0.39 g, yield: 30%). 1 H-NMR (400MHz, CDCl3): δ7.87(d,J=8.2Hz,1H),7.85(d,J=1.8Hz,1H),7.54-7.51(m,3H),7.00-6.97(m,2H),3.94(s,3H),3.85(s,3H). To a solution of methyl 2-bromo-4-(4-methoxyphenyl)benzoate (2.10 g, 6.50 mmol) in THF (10 mL), water (10 mL) and sodium hydroxide (1.30 g, 32.5 mmol) were added, and the mixture was stirred at 50°C for 5 hours. After the reaction was complete, the solution was concentrated and washed with ethyl acetate. The resulting aqueous layer was acidified with 2 M hydrochloric acid, the precipitated solid was filtered, washed with water, and then dried under reduced pressure to obtain a white solid of 2-bromo-4-(4-methoxyphenyl)benzoic acid (yield: 1.76 g, yield: 88%). 1 H-NMR (400MHz, DMSO-d6): δ7.95(d,J=1.7Hz,1H),7.84(d,J=8.0Hz,1H),7.75-7.70(m,3H),7.07-7.05(m,2H),3.82(s,3H). Under an argon atmosphere, 1.70 g, 5.53 mmol of 2-bromo-4-(4-methoxyphenyl)benzoic acid was dissolved in toluene (10 mL), to which 4.0 mL, 55.3 mmol of thionyl chloride and 5.0 μL of DMF were added, and the mixture was stirred at 100 °C for 1 hour. Then, thionyl chloride was removed under reduced pressure, and 10 mL of dichloromethane was added to the resulting residue. This entire solution was used in the next reaction.

[0215] Under an argon atmosphere, triethylamine (1.54 mL, 11.1 mmol) was added to a solution of N-methyl-p-anisidine (0.76 g, 5.53 mmol) in dichloromethane (10 mL) and cooled to 0°C. The previously prepared dichloromethane solution of acid chloride was added dropwise over 5 minutes. The mixture was heated to room temperature and stirred for 2 hours. Water was added to the resulting mixture and extracted with dichloromethane. The organic layer was washed with saturated sodium bicarbonate aqueous solution, 2 M hydrochloric acid, and water, and then dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 64:36) to obtain a pale yellow solid of 2-bromo-4'-methoxy-N-(methoxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (yield: 2.00 g, yield: 85%). 1H-NMR (400MHz, CDCl3): δ7.57-7.56(d,J=1.8Hz,1H),7.41-7.39(m,2H),7.27(m,1H),7.12 -7.09(m,3H),6.93-6.91(m,2H),6.71-6.69(m,2H),3.82(s,3H),3.70(s,3H),3.47(s,3H). Under an argon atmosphere, a solution of 2-bromo-4'-methoxy-N-(methoxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (1.85 g, 4.34 mmol) in dichloromethane (22 mL) was cooled to 0°C. Then, a 1 M boron tribromide dichloromethane solution (13.0 mL, 13.0 mmol) was added dropwise, and the reaction system was raised to room temperature and stirred for 15 hours. After the reaction was complete, the solution was cooled again to 0°C, ice (100 g) was added, and the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure to remove the dichloromethane, and extracted with ethyl acetate. The mixture was then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate = 36:64), and the resulting solid was washed with chloroform to obtain a pale pink solid of 2-bromo-4'-hydroxy-N-(hydroxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (compound 17) (yield: 1.66 g, yield: 96%). 1 H-NMR (400MHz, DMSO-d6): δ9.59(brs,2H),7.63(d,J=1.6Hz,1H),7.46-7.40(m,3H),7.24(d,J =8.3Hz,1H),7.08(d,J=9.1Hz,2H),6.80(d,J=9.1Hz,2H),6.58(d,J=8.7Hz,2H),3.31(s,3H). [Monomer Example 18]

[0216] [ka]

[0217] Under an argon atmosphere, 60 mL of a 6.00 g, 27.6 mmol solution of 4-bromo-2-hydroxybenzoic acid was mixed with thionyl chloride (10.0 mL, 138 mmol) and DMF (3 drops), and the mixture was stirred at room temperature for 48 hours. Then, thionyl chloride was removed under reduced pressure, and 30 mL of dichloromethane was added to the resulting residue. This entire solution was used in the next reaction.

[0218] Under an argon atmosphere, triethylamine (5.74 mL, 41.4 mmol) was added to a solution of N-methyl-p-anisidine (1.89 g, 13.8 mmol) in dichloromethane (30 mL) and cooled to 0°C. The previously prepared dichloromethane solution of acid chloride was added dropwise over 5 minutes. The mixture was heated to room temperature and stirred for 6 hours. After the reaction was complete, the reaction mixture was concentrated, and THF (20 mL), water (20 mL), and sodium hydroxide (2.2 g, 55.2 mmol) were added and stirred at 50°C for 5 hours. After the reaction was complete, the reaction mixture was concentrated, water was added, and it was extracted with ethyl acetate. The organic layer was then washed with 2 M hydrochloric acid, saturated sodium bicarbonate aqueous solution, and water, and dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure to obtain a brown solid of 2-hydroxy-4-bromo-4'-methoxy-N-methylbenzanilide (yield: 4.22 g, yield: 91%). 1 H-NMR (400MHz, CDCl3): δ11.4(brs,1H),7.10(d,J=1.8Hz,1H),7.04-7.00(m,2H),6.87-6.83(m,2H),6.55-6.49(m,2H),3.80(s,3H),3.42(s,3H). Under an argon atmosphere, potassium carbonate (3.37 g, 24.4 mmol), 4-methoxyphenylboronic acid (2.04 g, 13.4 mmol), and tetrakistriphenylphosphine palladium (0) (0) were added to a solution of 2-hydroxy-4-bromo-4'-methoxy-N-methylbenzanilide (4.10 g, 12.2 mmol) in toluene (18 mL) and water (18 mL), and the mixture was stirred at 100 °C for 3 hours. After the reaction was complete, water was added and the mixture was extracted with ethyl acetate. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 80:20) to obtain an orange oily substance of 2-hydroxy-4'-methoxy-N-(4-methoxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (yield: 2.98 g, yield: 67%). 1 H-NMR (400MHz, CDCl3): δ11.4(brs,1H),7.48-7.44(m,2H),7.12(d,J=1.8Hz,1H),7.07-7.04(m,2H),6.92- 6.89(m,2H),6.86-6.83(m,2H),6.70(d,J=8.5Hz,1H),6.63(m,1H),3.81(s,3H),3.78(s,3H),3.44(s,3H). Under an argon atmosphere, a 40 mL solution of 2-hydroxy-4'-methoxy-N-(4-methoxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (2.98 g, 8.2 mmol) in dichloromethane was cooled to 0°C, and diisopropylethylamine (1.66 mL, 9.84 mmol) was added and the mixture was stirred for 10 minutes. Then, trifluoromethanesulfonic anhydride (1.74 mL, 10.7 mmol) was added dropwise, and the reaction temperature was raised to room temperature and stirred for 15 hours. After the reaction was complete, the mixture was washed with saturated sodium bicarbonate aqueous solution and water, and the aqueous layer was re-extracted with dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 80:20) to obtain an orange oily substance of 2-trifluoromethanesulfonyloxy-4'-methoxy-N-(4-methoxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (yield: 3.44 g, yield: 84%). 1 H-NMR (400MHz, CDCl3): δ7.42-7.38(m,4H),7.21(s,1H),7.00(d,J=9.0Hz,2H),6. 93(d,J=9.0Hz,2H),6.71(d,J=9.0Hz,2H),3.82(s,3H),3.71(s,3H),3.46(s,3H). 19 F-NMR (376MHz, CDCl3): δ-73.5(s). Under an argon atmosphere, a solution of 2-trifluoromethanesulfonyloxy-4'-methoxy-N-(4-methoxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (3.43 g, 6.92 mmol) in dichloromethane (35 mL) was cooled to 0°C. Then, a 1 M boron tribromide dichloromethane solution (21.0 mL, 21.0 mmol) was added dropwise, and the reaction system was raised to room temperature and stirred for 15 hours. After the reaction was complete, the solution was cooled again to 0°C, ice (100 g) was added, and the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure to remove the dichloromethane, and extracted with ethyl acetate. The mixture was then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 5:95) to obtain a pale yellow solid of 2-trifluoromethanesulfonyloxy-4'-hydroxy-N-(4-hydroxyphenyl)-N-methyl[1,1'-biphenyl]-4-carboxamide (compound 18) (yield: 3.06 g, yield: 95%). 1 H-NMR (400MHz, DMSO-d6): δ9.79(brs,1H),9.58(brs,1H),7.59(d,J=7.8Hz,1H),7.51(d,J=7.8Hz,2H),7.44( d,J=7.8Hz,1H),7.40(s,1H),6.97(d,J=8.5Hz,2H),6.83(d,J=8.5Hz,2H),6.59(d,J=8.5Hz,2H),3.31(s,3H). 19 F-NMR (376MHz, DMSO-d6): δ-73.6(s). [Monomer Example 19]

[0219] [ka]

[0220] Under an argon atmosphere, thionyl chloride (7.76 mL, 107 mmol) and DMF (50 μL) were added to a solution of 4-bromo-2-chlorobenzoic acid (2.52 g, 10.7 mmol) in toluene (20 mL), and the mixture was stirred at 100°C for 1 hour. Then, thionyl chloride was removed under reduced pressure, and dichloromethane (20 mL) was added to the resulting residue. This entire solution was used in the next reaction.

[0221] Under an argon atmosphere, triethylamine (2.96 mL, 21.4 mmol) was added to a solution of 4-bromo-N-methylaniline (2.00 g, 10.7 mmol) in dichloromethane (20 mL) and cooled to 0°C. The previously prepared dichloromethane solution of acid chloride was added dropwise over 5 minutes. The mixture was heated to room temperature and stirred for 3 hours. Water was added to the resulting mixture and extracted with dichloromethane. The organic layer was washed with saturated sodium bicarbonate aqueous solution, 2 M hydrochloric acid, and water, and then dried over anhydrous sodium sulfate. The resulting solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate = 90:10) to obtain a brown oily substance of 4,4'-dibromo-2-chloro-N-methylbenzanilide (yield: 3.72 g, yield: 86%). 1 H-NMR (400MHz, CDCl3): δ7.37(d,J=1.4Hz,1H),7.31(d,J=8.6Hz,2H),7.22(m,1H),6.99(d,J=8.4Hz,1H),6.95(d,J=8.4Hz,2H),3.44(s,3H). Under an argon atmosphere, potassium carbonate (2.74 g, 19.8 mmol), 4-methoxyphenylboronic acid (1.66 g, 10.9 mmol), and tetrakistriphenylphosphine palladium (0) (0) (0.086 g, 0.074 mmol) were added to a solution of 4,4'-bromo-2-chloro-N-methylbenzanilide (2.00 g, 4.96 mmol) in toluene (15 mL) and water (15 mL), and the mixture was stirred at 100 °C for 8 hours. After the reaction was complete, water was added and the mixture was extracted with chloroform. The combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:chloroform = 6:94) to obtain a pale yellow solid of 2-chloro-4'-methoxy[1,1'-biphenyl]-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (yield: 1.97 g, yield: 87%). 1 H-NMR (400MHz, CDCl3): δ7.43-7.37(m,7H),7.25(m,1H),7.20-7.16(m,3H),6.92-6.90(m,4H),3.81(s,6H),3.54(s,3H). Under an argon atmosphere, a solution of 2-chloro-4'-methoxy[1,1'-biphenyl]-N-(4'-methoxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (1.74 g, 3.80 mmol) in dichloromethane (20 mL) was cooled to 0°C. Then, a 1 M boron tribromide dichloromethane solution (11.4 mL, 11.4 mmol) was added dropwise, and the reaction system was raised to room temperature and stirred for 15 hours. After the reaction was complete, the solution was cooled again to 0°C, ice (100 g) was added, and the mixture was stirred at room temperature until the ice dissolved. The mixture was concentrated under reduced pressure to remove the dichloromethane, and the precipitated solid was filtered and washed with water. The obtained solid was reprecipitated with water (100 mL)-DMF (4.0 mL) to obtain a white solid of 2-chloro-4'-hydroxy[1,1'-biphenyl]-N-(4'-hydroxy[1,1'-biphenyl]-4-yl)-N-methylbenzamide (compound 19) (yield: 1.32 g, yield: 81%). 1H-NMR (400MHz, DMSO-d6): δ9.64(brs,2H),7.52-7.39(m,8H),7.35(d,J=8.1Hz,1H),7.26(d,J=8.5Hz,2H),6.79-6.76(m,4H),3.40(s,3H). [Example 1]

[0222] [ka]

[0223] In a 200 ml three-necked flask equipped with a dropping funnel, 20 ml of deionized water was placed, and compound 1 (1.11 g, 4.00 mmol) synthesized in monomer example 1 and sodium hydroxide (320 mg, 8.00 mmol) were dissolved and stirred. A 2% aqueous solution of tetrabutylammonium bromide (1.6 mL) was added as a catalyst, and the apparatus was thoroughly purged with nitrogen. A solution of terephthalic acid chloride (812 mg, 4.00 mmol) dissolved in 20 ml of dichloromethane was placed in the dropping funnel and gently added dropwise. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. The reaction solution was added to methanol, the precipitate was filtered off, washed with methanol, and then vacuum dried to obtain polymer 1 (yield: 1.80 g, quantitative).

[0224] 5.0% by mass of polymer 1 was dissolved in 95.0% by mass of a chloroform:pentafluorophenol (2:1) mixed solvent. This was cast onto a quartz glass substrate and spin-coated at 1500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0225] [Example 1-1] 5.0% by mass of polymer 1 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoro-2-propanol. This was cast onto a quartz glass substrate and spin-coated at 4000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). The obtained thin film was exposed to polarized ultraviolet light at 313 nm at 500 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0226] [Examples 1-2] 5.0% by mass of polymer 1 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoro-2-propanol. This was cast onto a quartz glass substrate and spin-coated at 5000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). The obtained thin film was exposed to polarized ultraviolet light at 248 nm at 500 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0227] [Example 2]

[0228] [ka]

[0229] Under an argon atmosphere, trans-1,4-cyclohexanedicarboxylic acid (689 mg, 4.00 mmol) was mixed with thionyl chloride (6 mL) and DMF (10 μL), and the mixture was stirred at 80°C for 4 hours. After that, thionyl chloride was removed by distillation under reduced pressure (evaporator, 80°C), and the mixture was dried using a vacuum pump to obtain trans-1,4-cyclohexanedicarboxylic acid dichloride. The entire amount of this compound was used in the following reaction.

[0230] 20 mL of deionized water was placed in a 200 mL three-necked flask equipped with a dropping funnel, and compound 1 (1.11 g, 4.00 mmol) synthesized in monomer example 1 and sodium hydroxide (320 mg, 8.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 1.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A 20 mL solution of trans-1,4-cyclohexanedicarboxylic acid dichloride prepared above was placed in the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (200 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 1.04 g of polymer 2 as a white solid in a yield of 63%. 1 H-NMR (400MHz, CDCl3): δ7.21-6.79(brm,7H),3.54-3.41(br,3H),2.62-2.41(br,2H),2.36-2.14(br,4H),1.68-1.50(br,4H). 6.0% by mass of polymer 2 was dissolved in 94.0% by mass of 1,1,1,3,3,3-hexafluoro-2-propanol. This was cast onto a quartz glass substrate and spin-coated at 1700 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 254 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 270°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0231] [Example 3]

[0232] [ka]

[0233] In a 200 ml three-necked flask equipped with a dropping funnel, 20 ml of deionized water was placed, and compound 2 (1.11 g, 4.00 mmol) synthesized in monomer example 2 and sodium hydroxide (320 mg, 8.00 mmol) were dissolved and stirred. A 2% aqueous solution of tetrabutylammonium bromide (1.6 mL) was added as a catalyst, and the apparatus was thoroughly purged with nitrogen.

[0234] A solution of terephthalate chloride (812 mg, 4.0 mmol) dissolved in 20 ml of dichloromethane was placed in a dropping funnel and slowly added dropwise.

[0235] After the dropwise addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. The reaction solution was added to methanol, the precipitate was filtered off and washed with methanol, and then vacuum dried to obtain 1.63 g of polymer 3 as a white solid in 99% yield.

[0236] 5.0% by mass of polymer 3 was dissolved in 95.0% by mass of a chloroform:pentafluorophenol (2:1) mixed solvent. This was cast onto a quartz glass substrate and spin-coated at 1400 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 170°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0237] [Example 4]

[0238] [ka]

[0239] In a 200 mL three-necked flask equipped with a dropping funnel, 20 mL of deionized water was placed, and compound 3 (1.11 g, 4.00 mmol) synthesized in monomer example 3 and sodium hydroxide (320 mg, 8.00 mmol) were dissolved and stirred. A 2% aqueous solution of tetrabutylammonium bromide (1.6 mL) was added as a catalyst, and the apparatus was thoroughly purged with nitrogen.

[0240] A solution of terephthalate chloride (0.812 g, 4.0 mmol) dissolved in 20 mL of dichloromethane was placed in a dropping funnel and slowly added dropwise.

[0241] After the dropwise addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. The reaction solution was added to methanol, the precipitate was filtered off and washed with methanol, and then vacuum dried to obtain 0.49 g of polymer 3 as a white solid in a yield of 30%.

[0242] 6.0% by mass of polymer 4 was dissolved in 94.0% by mass of a chloroform:pentafluorophenol (2:1) mixed solvent. This was cast onto a quartz glass substrate and spin-coated at 3000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 150°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0243] [Example 5]

[0244] [ka]

[0245] 20 mL of deionized water was placed in a 200 mL three-necked flask equipped with a dropping funnel, and compound 4 (1.28 g, 4.00 mmol) synthesized in monomer example 4 and sodium hydroxide (320 mg, 8.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 1.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A solution of terephthalic acid chloride (812 mg, 4.00 mmol) in dichloromethane (20 mL) was placed in the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred (350 rpm) at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (200 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 1.63 g of polymer 5 as a white solid in 91% yield. 1 H-NMR (400MHz, CDCl3): δ8.37-8.10(brm,4H),7.55-6.93(brm,7H),4.05-3.85(br,2H),1.74-1.58(brm,2H),1.51(brm,2H),1.03-0.90(brm,3H). 6.0% by mass of polymer 5 was dissolved in 94.0% by mass of chloroform. This was cast onto a quartz glass substrate and spin-coated at 2000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 130°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0246] [Example 6]

[0247] [ka]

[0248] 20 mL of deionized water was placed in a 200 mL three-necked flask equipped with a dropping funnel, and compound 5 (1.50 g, 4.00 mmol) synthesized in monomer example 5 and sodium hydroxide (320 mg, 8.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 1.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A solution of terephthalic acid chloride (812 mg, 4.00 mmol) in dichloromethane (20 mL) was placed in the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (200 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 1.92 g of polymer 6 as a white solid in 95% yield. 1 H-NMR (400MHz, CDCl3): δ8.38-8.12(brm,4H),7.55-6.45(brm,7H),4.02-3.85(br,2H),1.75-1.06(brm,12H),0.94-0.81(brm,3H). 6.0% by mass of polymer 6 was dissolved in 94.0% by mass of chloroform. This was cast onto a quartz glass substrate and spin-coated at 3000 rpm for 60 seconds. A thin film (thickness 1 μm) was dried in an oven at 150°C for 30 minutes. Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 90°C resulted in a high phase difference. The phase difference is shown in Table 1.

[0249] [Example 7]

[0250] [ka]

[0251] In a 200 mL three-necked flask equipped with a dropping funnel, 20 mL of deionized water was added, and 1.78 g (4.00 mmol) of 2,5-dichloro-N,N'-bis(hydroxyphenyl)-N,N'-dimethyl-1,4-benzenedicaramide and 320 mg (8.00 mmol) of sodium hydroxide were added. After dissolving the substrate by vigorous stirring (350 rpm), 1.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A 20 mL solution of terephthalate chloride (812 mg, 4.00 mmol) in dichloromethane was taken into the dropping funnel and rapidly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (150 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum-dried to obtain 2.11 g of the white solid JST-19088 in 92% yield. 1 H-NMR (400MHz, CDCl3): δ8.32-7.75(brm,4H),7.55-6.99(brm,10H),3.58-3.09(brm,6H). 6.0% by mass of polymer 7 was dissolved in 94.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 7000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 200°C resulted in the appearance of a high phase difference. The phase difference is shown in Table 1.

[0252] [Example 8]

[0253] [ka]

[0254] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 7 (983 mg, 3.00 mmol) synthesized in monomer example 7 and sodium hydroxide (240 mg, 6.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 1.2 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A solution of terephthalic acid chloride (609 mg, 3.00 mmol) in dichloromethane (15 mL) was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 1.33 g of polymer 8 as a white solid in 97% yield.

[0255] 5.0% by mass of polymer 8 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 7000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 190°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0256] [Example 9]

[0257] [ka]

[0258] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 8 (418 mg, 1.50 mmol) synthesized in monomer example 8 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 578 mg of polymer 9 as a white solid in a yield of 94%.

[0259] 6.0% by mass of polymer 9 was dissolved in 94.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 4000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 220°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0260] [Example 10]

[0261] [ka]

[0262] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 9 (492 mg, 1.50 mmol) synthesized in monomer example 9 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 666 mg of polymer 10 as a white solid in 97% yield.

[0263] 4.5% by mass of polymer 10 was dissolved in 95.5% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 3000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0264] [Example 11]

[0265] [ka]

[0266] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 10 (531 mg, 1.50 mmol) synthesized in monomer example 10 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% tetrabutylammonium bromide aqueous solution was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 698 mg of polymer 11 as a white solid in 96% yield.

[0267] 6.0% by mass of polymer 11 was dissolved in 94.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 3000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0268] [Example 12]

[0269] [ka]

[0270] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 11 (492 mg, 1.50 mmol) synthesized in monomer example 11 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% tetrabutylammonium bromide aqueous solution was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 640 mg of polymer 12 as a white solid in 93% yield.

[0271] 5.0% by mass of polymer 12 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 1500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 150°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0272] [Example 13]

[0273] [ka]

[0274] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 12 (492 mg, 1.50 mmol) synthesized in monomer example 12 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 667 mg of polymer 13 as a white solid in a yield of 97%.

[0275] 5.0% by mass of polymer 13 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 1500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0276] [Example 14]

[0277] [ka]

[0278] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 13 (597 mg, 1.50 mmol) synthesized in monomer example 13 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 746 mg of polymer 14 as a white solid in a yield of 94%.

[0279] 5.0% by mass of polymer 14 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 1500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0280] [Example 15]

[0281] [ka]

[0282] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 14 (587 mg, 1.50 mmol) synthesized in monomer example 14 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 640 mg of polymer 15 as a white solid in 82% yield.

[0283] 5.0% by mass of polymer 15 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 1500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 150°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0284] [Example 16]

[0285] [ka]

[0286] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 15 (701 mg, 1.50 mmol) synthesized in monomer example 15 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% tetrabutylammonium bromide aqueous solution was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 531 mg of polymer 16 as a white solid in a yield of 59%.

[0287] 5.0% by mass of polymer 16 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 3000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 190°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0288] [Example 17]

[0289] [ka]

[0290] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 16 (531 mg, 1.50 mmol) synthesized in monomer example 16 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 693 mg of polymer 17 as a white solid in 95% yield.

[0291] 5.0% by mass of polymer 17 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 5000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0292] [Example 18]

[0293] [ka]

[0294] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 17 (597 mg, 1.50 mmol) synthesized in monomer example 17 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 710 mg of polymer 18 as a white solid in a yield of 66%.

[0295] 5.0% by mass of polymer 18 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 2500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0296] [Example 19]

[0297] [ka]

[0298] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 18 (701 mg, 1.50 mmol) synthesized in monomer example 18 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 794 mg of polymer 19 as a white solid in 88% yield.

[0299] 5.0% by mass of polymer 19 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 5000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 150°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0300] [Example 20]

[0301] [ka]

[0302] In a 200 mL three-necked flask equipped with a dropping funnel, 15 mL of deionized water was added, and compound 19 (645 mg, 1.50 mmol) synthesized in monomer example 19 and sodium hydroxide (120 mg, 3.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.6 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (305 mg, 1.50 mmol) in 15 mL was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 755 mg of polymer 20 as a white solid in a yield of 67%.

[0303] 4.5% by mass of polymer 20 was dissolved in 95.5% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 2000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0304] [Example 20-1] 5.0% by mass of polymer 1 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoro-2-propanol. This was cast onto a quartz glass substrate and spin-coated at 2500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). The obtained thin film was exposed to polarized ultraviolet light at 313 nm at 500 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0305] [Example 20-2] 5.0% by mass of polymer 1 was dissolved in 95.0% by mass of 1,1,1,3,3,3-hexafluoro-2-propanol. This was cast onto a quartz glass substrate and spin-coated at 2500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). The obtained thin film was exposed to polarized ultraviolet light at 248 nm at 500 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0306] [Example 21]

[0307] [ka]

[0308] In a 200 mL three-necked flask equipped with a dropping funnel, 20 mL of deionized water was added, and compound 10 (708 mg, 2.00 mmol) synthesized in monomer example 10 and sodium hydroxide (160 mg, 4.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.8 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of trans-cyclohexanedicarboxylic acid chloride (418 mg, 2.00 mmol) was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain 833 mg of polymer 21 as a white solid in 85% yield.

[0309] 4.5% by mass of polymer 21 was dissolved in 95.5% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 2500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 248 nm was applied to the obtained thin film at a rate of 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0310] [Example 22]

[0311] [ka]

[0312] In a 200 mL three-necked flask equipped with a dropping funnel, 20 mL of deionized water was added, and Compound 1 (500 mg, 1.80 mmol) synthesized in Monomer Example 1, diethylene glycol (21.2 mg, 0.20 mmol), and sodium hydroxide (160 mg, 4.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.8 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (406 mg, 2.00 mmol) was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum-dried to obtain 758 mg of polymer 22 as a white solid in 96% yield.

[0313] 4.5% by mass of polymer 22 was dissolved in 95.5% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 4500 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 248 nm was applied to the obtained thin film at a rate of 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0314] [Example 23]

[0315] [ka]

[0316] In a 200 mL three-necked flask equipped with a dropping funnel, 20 mL of deionized water was added, and compound 10 (637 mg, 1.80 mmol) synthesized in monomer example 10, diethylene glycol (21.2 mg, 0.20 mmol), and sodium hydroxide (160 mg, 4.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.8 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of terephthalic acid chloride (406 mg, 2.00 mmol) was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum-dried to obtain 777 mg of polymer 23 as a white solid in 85% yield.

[0317] 4.5% by mass of polymer 23 was dissolved in 95.5% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 1900 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). Polarized ultraviolet light at 248 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0318] [Example 24]

[0319] [ka]

[0320] In a 200 mL three-necked flask equipped with a dropping funnel, 20 mL of deionized water was added, and Compound 1 (444 mg, 1.60 mmol) synthesized in Monomer Example 1, hydroquinone (44.0 mg, 0.40 mmol), and sodium hydroxide (160 mg, 4.00 mmol) were added. After dissolving the substrate by vigorous stirring (350 rpm), 0.8 mL of 2% aqueous solution of tetrabutylammonium bromide was added as a catalyst, and the apparatus was thoroughly purged with argon. A chloroform solution of trans-cyclohexanedicarboxylic acid chloride (406 mg, 2.00 mmol) was taken into the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was vigorously stirred at room temperature for 3 hours to carry out interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL), the precipitate was filtered off, washed with water (100 mL) and methanol (100 mL), and then vacuum-dried to obtain 1.19 g of polymer 24 as a white solid in a yield of 78%.

[0321] 7.0% by mass of polymer 24 was dissolved in 93% by mass of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 1600 rpm, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 1 μm). The obtained thin film was exposed to polarized ultraviolet light at 248 nm at 500 mJ / cm². 2 After irradiation, heating at 250°C resulted in the emergence of a high phase difference. The phase difference is shown in Table 1.

[0322] [Comparative Example 1]

[0323] [ka]

[0324] Under a nitrogen atmosphere, a mixture of 4-methoxy-N-methylaniline (3.00 g, 21.9 mmol), tetrahydrofuran (20 mL), and water (20 mL) was cooled on ice, and then sodium bicarbonate (11 g) was added. While stirring the mixture, a solution of terephthalic acid chloride (2.17 g, 10.7 mmol) in tetrahydrofuran (20 mL) was slowly added, and the mixture was stirred on ice for 3 hours. Water (500 mL) was added to the reaction mixture, and the resulting solid was filtered off. The mixture was then washed with 2N hydrochloric acid (200 mL) and methanol (300 mL) to obtain N,N'-bis(4-methoxyphenyl)-N,N'-dimethyl-1,4-benzenedicarboxamide (yield: 3.91 g, yield: 90%). 1 H-NMR (400MHz, (CD3)2SO): δ7.07(s,4H),6.83(d,J=8.0Hz,4H),6.67(d,J=8.0Hz,4H),3.73(s,6H),3.38(s,6H). The N,N'-bis(4-methoxyphenyl)-N,N'-dimethyl-1,4-benzenedicaramide (1.00 g, 2.47 mmol) obtained above was dissolved in dichloromethane (25 mL), and then 1 mol / L boron tribromide dichloromethane solution (7.4 mL) was added over 5 minutes under ice cooling. After raising the reaction system to room temperature, it was stirred for 15 hours, and the reaction mixture was added to ice-cooled water (300 mL). The solid formed in the system was filtered and washed with water (500 mL) to obtain the brown solid of compound 1' (yield: 776 mg, yield: 83%). 1 H-NMR (400MHz, (CD3)2SO): δ9.55-9.28(br,2H),6.98(s,4H),6.87-6.67(m,4H),6.58-6.49(m,4H),3.20(s,6H). In a three-necked flask equipped with a dropping funnel, 6.5 ml of water was placed, and compound 1' (1.3 mmol) and sodium hydroxide (2.6 mmol) were dissolved and stirred. 0.5 ml of a 2.0 wt% aqueous solution of tetra-n-butylammonium bromide was added as a catalyst, and the apparatus was purged with nitrogen. A solution of terephthalic acid chloride (1.3 mmol) dissolved in 6.5 ml of dichloromethane was placed in the dropping funnel and added dropwise, followed by stirring at room temperature for 3 hours. The reaction solution was added to methanol, the precipitate was filtered off, and polymer 1' was obtained by vacuum drying (yield 99%).

[0325] Polymer 1' of Comparative Example 1, at a concentration of 3.0% by mass, was dissolved in 97.0% by mass chloroform. This was cast onto a quartz substrate and spin-coated at 7000 rpm for 60 seconds. A thin film was then dried in an oven at 150°C for 30 minutes. The resulting thin film (thickness 1 μm) was exposed to polarized ultraviolet light at 248 nm at a rate of 500 mJ / cm². 2 After irradiation, when heated at 250°C, polymer 1' of Comparative Example 1 did not exhibit a high phase difference. The phase difference is shown in Table 1.

[0326] [Table 1]

[0327] As is clear from Table 1, the polymers of Examples 1 to 23 were confirmed to exhibit a large phase difference (Re) upon irradiation with ultraviolet light and heat calcination treatment. The unique performance of the polymers of this application becomes even more apparent when compared with Comparative Example 1.

[0328] [Example 25] 3% by mass of polymer 11 was dissolved in 97% by mass of 1,1,1,3,3,3-hexafluoro-2-propanol. This was cast onto a quartz glass substrate and spin-coated at 5000 rpm for 60 seconds, then dried in an oven at 150°C for 30 minutes to obtain a thin film (thickness 0.5 μm). Polarized ultraviolet light at 313 nm was applied to the obtained thin film at 7200 mJ / cm². 2 After irradiation, the liquid crystal alignment film was created by heating at 250°C.

[0329] Two 25μm thick PET films (Toray Industries, product name: Lumirror(R) T60) cut to 1.5mm x 20mm were used as spacers. Two quartz glass plates on which the liquid crystal alignment film was laminated were stacked with the thin film facing inward and the direction of irradiation with polarized ultraviolet light parallel to each other. Instant adhesive (Toagosei, Aron Alpha 201) was used to bond the periphery of the quartz glass plates, excluding the area that would become the liquid crystal injection port, to form a liquid crystal empty cell. After bonding, 4-cyano-4'-pentylbiphenyl heated at 50°C was injected into the liquid crystal empty cell to form a liquid crystal cell. The obtained liquid crystal cell was observed using a polarizing microscope in three directions, with the polarizer angles being 0°, 45°, and 90° relative to the direction in which polarized ultraviolet light was irradiated onto the thin film. The microscope image changed from dark to light to dark, confirming that the liquid crystal directors were uniformly aligned. [In this specification, "liquid crystal director" refers to the vector of the direction in which the long axis of a liquid crystalline molecule is oriented (principal axis of orientation).] [Comparative Example 2] 10.0% by mass of methyl methacrylate polymer was dissolved in 90.0% by mass of toluene. This was cast onto a quartz glass substrate and spin-coated at 5000 rpm for 60 seconds. A thin film (thickness 0.5 μm) was dried in an oven at 150°C for 30 minutes. The obtained thin film was exposed to polarized ultraviolet light at 248 nm at a rate of 500 mJ / cm². 2 After irradiation, the film (hereinafter referred to as "this film") was created by heating at 250°C.

[0330] Two 25μm thick PET films (Toray Industries, product name: Lumirror(R) T60) cut to 1.5mm x 20mm were used as spacers. Two quartz glass plates on which the thin film was laminated were then stacked with the thin film facing inward and the direction of irradiation with polarized ultraviolet light parallel to each other. Instant adhesive (Toagosei, Aron Alpha 201) was used to bond the periphery of the quartz glass plates, excluding the area that would become the liquid crystal injection port, to form a liquid crystal cell. After bonding, 4-cyano-4'-pentylbiphenyl heated at 50°C was injected into the liquid crystal cell to form a liquid crystal cell. The obtained liquid crystal cell was observed using a polarizing microscope in three directions, with the polarizer angles being 0°, 45°, and 90° relative to the direction in which the polarized ultraviolet light was irradiated onto the thin film. The microscope image remained bright at all times, confirming that the liquid crystal director was not uniformly aligned.

[0331] The fact that the thin film of Example 25 can be used as a liquid crystal alignment film by irradiating it with ultraviolet light and performing a heat firing treatment becomes even more evident when compared with Comparative Example 2.

Claims

1. A photoreactive polymer in which a constituent unit containing a photoreactive structure undergoes a chemical reaction upon light irradiation, wherein the photoreactive structure is represented by the following formula (1). 【Chemistry 1】 [In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. R １ and R ２ This represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group, which may be the same or different in nature. X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. S １ and S ２ Each of these independently represents a spacer group or a single bond. The spacer group is -CH ２ -ien-CH ２ CH ２ -, -O-, -C(=O)-, -NH-, or alkylene groups having 3 to 20 carbon atoms, and represents a group selected from the group consisting of -, -O-, -C(=O)-, -NH-, or alkylene groups having 3 to 20 carbon atoms, and the alkylene group has two or more non-adjacent -CH groups. ２ Each of the hyphens can be independently replaced with -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-. n represents 0 or 1.

2. In the formula (1), ring A, ring B, and ring C are each an optionally substituted aromatic ring having atoms selected from the group consisting of carbon atoms and nitrogen atoms as ring-constituting atoms, an optionally substituted polycyclic aromatic ring, or an optionally substituted condensed aromatic ring, and R １ and R ２ may be the same or different and are each a group selected from the group consisting of a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. The photoreactive polymer according to claim 1.

3. The photoreactive polymer according to claim 1 or 2, having a photoreactive structure represented by formula (1) and a structure represented by the following formula (2). 【Chemistry 2】 [In the formula, ring D represents a ring selected from the group consisting of an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, the ring constituent atoms being selected from the group consisting of an alicyclic hydrocarbon ring, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and these alicyclic hydrocarbon rings, aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. S ３ and S ４ Each of these independently represents a spacer group or a single bond. The spacer group is -CH ２ -ien-CH ２ CH ２ -, -O-, -C(=O)-, -NH-, or alkylene groups having 3 to 20 carbon atoms, and represents a group selected from the group consisting of -, -O-, -C(=O)-, -NH-, or alkylene groups having 3 to 20 carbon atoms, and the alkylene group has two or more non-adjacent -CH groups. ２ Each of the hyphens can be independently replaced with -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-.

4. A method for producing a photoreactive polymer, comprising subjecting the photoreactive polymer according to any one of claims 1 to 3 to ultraviolet irradiation treatment, which is either polarized ultraviolet light or obliquely incident ultraviolet light.

5. A polymer containing the constituent units represented by the following formula (1'). 【Transformation 3】 [In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. R1 and R2 may be the same or different, and represent a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C20 alkyl group, an optionally substituted C3 to C8 cycloalkyl group, or an optionally substituted aromatic group. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. S1 and S2 each independently represent a spacer group or a single bond. The spacer group represents a group selected from the group consisting of -CH₂-, -CH₂CH₂-, -O-, -C(=O)-, -NH-, or alkylene groups having 3 to 20 carbon atoms, and two or more non-adjacent -CH₂- in the alkylene group may each be independently replaced with -O-, -(C=O)O-, -O(C=O)-, -O(C=O)-O-, -C(=O)-NH-, -NH-(C=O)-, -CH=CH-, or -C≡C-. n represents 0 or 1.

6. A method for producing a photoreactive polymer according to any one of claims 1 to 3, comprising copolymerizing a monomer represented by the following formula (3). 【Chemistry 4】 [In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. R １ and R ２ This represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group, which may be the same or different in nature. X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. F １ and F ２ Each of these independently represents a group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, or an isocyanate group. n represents 0 or 1.

7. In formula (3), rings A, B, and C are optionally substituted aromatic rings, optionally substituted polycyclic aromatic rings, or optionally substituted fused aromatic rings, wherein the ring constituent atoms are atoms selected from the group consisting of carbon atoms and nitrogen atoms. １ and R ２ The method for producing a photoreactive polymer according to claim 6, wherein the group is selected from the group consisting of a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may be the same or different in nature.

8. A method for producing a photoreactive polymer according to claim 6 or 7, wherein the monomer represented by formula (3) is a monomer represented by any of the following formulas (3-1-1) to (3-1-9) and (3-2-1). 【Transformation 5】 [In the formula, R １ and R ２ This represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group, which may be the same or different in nature. X ａ This represents a group selected from the group consisting of a halogen atom, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, or an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms. Y ａ represents a hydrogen atom or a halogen atom. F １ａ and F ２ａ Each of these independently represents either a hydroxyl group or an amino group.

9. A method for producing a photoreactive polymer according to any one of claims 6 to 8, wherein the monomer represented by formula (3) is a monomer represented by any one of the following formulas (3-1-1-1) to (3-2-1-3). 【Transformation 6】 [In the formula, R １ and R ２ This represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group, which may be the same or different in nature.

10. A method for producing a photoreactive polymer according to any one of claims 6 to 9, comprising copolymerizing a monomer represented by formula (3) with at least one copolymerization monomer selected from the group consisting of dicarboxylic acids, dicarboxylic acid chlorides, diamines, tetracarboxylic dianhydrides, polyvalent hydroxy compounds, and isocyanate compounds.

11. An optical film comprising a photoreactive polymer according to any one of claims 1 to 3 or 5.

12. The optical film according to claim 11, wherein the phase difference (Re) represented by the following formula (A), measured using a 589 nm light source by light irradiation and heat firing treatment, is 1 nm or more. Re=(ny-nx)×d (A) [In formula (A), nx represents the refractive index in the direction of the leading phase axis within the film plane, ny represents the refractive index in the direction of the slow phase axis within the film plane, and d represents the film thickness.]

13. The optical film according to claim 12, wherein the light irradiation treatment is performed by irradiating with one of the following types of ultraviolet light: polarized ultraviolet light and obliquely incident ultraviolet light.

14. A liquid crystal alignment film comprising the optical film according to any one of claims 11 to 13.

15. A resin composition comprising the photoreactive polymer described in any one of claims 1 to 3 or 5.

16. A monomer represented by the following formula (3). 【Transformation 7】 [In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, the ring constituent atoms of which are selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. R １ and R ２ This represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group, which may be the same or different in nature. X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. F １ and F ２ Each of these independently represents a group selected from the group consisting of a hydroxyl group, a carboxyl group, and an isocyanate group. n represents 0 or 1.

17. In formula (3), rings A, B, and C are optionally substituted aromatic rings, optionally substituted polycyclic aromatic rings, or optionally substituted fused aromatic rings, wherein the ring constituent atoms are atoms selected from the group consisting of carbon atoms and nitrogen atoms. １ and R ２ The monomer according to claim 16, wherein the group is selected from the group consisting of a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may be the same or different, and may be substituted.

18. F of the compound represented by the following formula (3') ３ and F ４ F １ and F ２ A method for producing a monomer according to claim 16 or 17, comprising the step of converting to a monomer. 【Transformation 8】 [In the formula, R １ , R ２ , A, B, C, X, Y, n, F １ and F ２ These are R in formula (3) above, respectively. １ , R ２ , A, B, C, X, Y, n, F １ and F ２ This is synonymous with F. ３ and F ４ Each of these independently represents a group selected from the group consisting of methoxy, methoxymethyloxy, benzyloxy, hydroxy, amino, carboxy, isocyanate, and nitro groups, and at least one of them is a group selected from the group consisting of methoxy, methoxymethyloxy, benzyloxy, and nitro groups.

19. A method for producing a monomer according to claim 18, wherein the monomer represented by formula (3) is the monomer represented by the following formula (3-1), and the compound represented by formula (3') is the compound represented by the following formula (3-1'). 【Chemistry 9】 [In the formula, R １ ,A,B,X,Y,F １ and F ２ These are R in formula (3) above, respectively. １ ,A,B,X,Y,F １ and F ２ This is synonymous with F. ３ and F ４ These are F in formula (3') above, respectively. ３ and F ４ This is synonymous with [the above].

20. A method for producing a monomer according to claim 19, comprising the step of producing a compound represented by formula (3-1') by reacting a carboxylic acid derivative represented by the following formula (4) with an amine compound represented by the following formula (5). 【Chemistry 10】 [In the formula, R １ A, B, X, and Y are R in formula (3) above, respectively. １ F is synonymous with A, B, X, and Y. ３ and F ４ These are F in formula (3') above, respectively. ３ and F ４ This is synonymous with [the leaving group]. Q represents a leaving group.

21. A method for producing a monomer represented by formula (3-1), The hydrogen atom on the nitrogen atom of the amide group adjacent to ring B of the amide compound shown in the following formula (3-1'') is R １ A step of producing a compound represented by the following formula (3-1') by substitution, 【Chemistry 11】 F of the compound represented by the following formula (3-1') ３ and F ４ F １ and F ２ A method for producing a monomer, comprising a step of converting it to a certain substance. 【Chemistry 12】 [In the formula, Ring A and Ring B each independently represent a ring selected from the group consisting of aromatic rings, polycyclic aromatic rings, or fused aromatic rings, with ring constituent atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. These aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have substituents. X represents a group selected from the group consisting of an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted C1 to C5 alkoxy group, a halogen atom, an optionally substituted C1 to C5 acyloxy group, an optionally substituted C1 to C5 alkylsulfonyloxy group, an optionally substituted C6 to C11 arylsulfonyloxy group, or an optionally substituted aryloxy group. F １ and F ２ Each of these independently represents a group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, and an isocyanate group. F ３ and F ４ Each of these independently represents a group selected from the group consisting of methoxy, methoxymethyloxy, benzyloxy, hydroxy, amino, carboxy, isocyanate, and nitro groups, and at least one of them is a group selected from the group consisting of methoxy, methoxymethyloxy, benzyloxy, and nitro groups. １ This represents an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, or an optionally substituted aromatic group.

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