Resin composition containing photoreactive polymer, optical thin film

Abstract

To provide a resin composition of a polymer that orients even under a low heating temperature of 200°C or lower, and develops a high phase difference such as a phase difference Re / thickness of 100 nm or more.SOLUTION: A resin composition contains 70 to 99.99 wt.% of a polymer containing 1 to 50 mol% of a structural unit represented by the following formula (1) and 0.01 to 30 wt.% of a thermal reorientation accelerator having a molecular weight of 200 to 10000. (In the formula, each of a ring A, a ring B and a ring C is independently a ring selected from the group consisting of monocyclic aromatic rings, polycyclic aromatic rings, and condensed ring aromatic rings having ring-constituting atoms selected from the group consisting of C, N, O, and S, and each of R1 and R2 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, etc., X is an alkoxy group having 1 to 5 carbon atoms, etc., Y is a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, etc., and each of S1 and S2 represents a spacer group or a single bond)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition containing a novel polymer, and further to an optical thin film using the same. More specifically, the present invention relates to an optical thin film that exhibits a high retardation even in a thin film by irradiation with ultraviolet light and heat baking treatment, for example, a resin composition containing a novel polymer suitable for a retardation film for a liquid crystal display element and an organic EL device, and an optical thin film using the same. [Background technology]

[0002] Retardation films are used in various image display devices to expand the viewing angle, among other things. Most existing retardation films are made using polymerizable liquid crystal compounds. To align the molecules of the polymerizable liquid crystal compound, an alignment film must be provided on the support on which the optically anisotropic layer is formed. For this purpose, alignment films that have undergone rubbing or photoalignment treatment are used (see, for example, Patent Documents 1 to 3). However, both methods require complex manufacturing equipment and processes, and there are also issues with product yield. Furthermore, proposals have been made to form optical thin films and retardation films that exhibit a retardation Re / thickness ratio of 100 nm or more by irradiating polarized ultraviolet light and heat treatment using side-chain liquid crystal acrylate resins containing photoreactive groups, without the need for an alignment film (see, for example, Patent Documents 4 and 5). However, side-chain liquid crystal acrylate resins containing photoreactive groups require multiple steps to synthesize the monomer, making them expensive, and they have problems such as low heat resistance. Linear liquid crystal polyester resins containing photoreactive groups can be used to form optical thin films and retardation films by irradiation with polarized ultraviolet light and heat treatment without the need for an alignment film. This makes it possible to manufacture optical thin films and retardation films with excellent heat resistance from inexpensive monomers. However, while linear liquid crystal polyester resins have excellent heat resistance, they require high processing temperatures of 200°C or higher (see, for example, Patent Documents 6 to 8). Therefore, when linear liquid crystal polyester resins are used as optical thin films and retardation films, they cannot be used with inexpensive, general-purpose resin film support substrates such as polyethylene terephthalate (heat-resistant temperature of approximately 160°C), polyethylene terenaphthalate (heat-resistant temperature of approximately 200°C), or cycloolefin polymer (heat-resistant temperature of approximately 160°C). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 8-160430 [Patent Document 2] Special Publication No. 2003-505561 [Patent Document 3] International Publication No. 2010 / 150748 Brochure [Patent Document 4] Japanese Patent Application Laid-Open No. 2002-226858 [Patent Document 5] International Publication No. 2014 / 017497 Brochure [Patent Document 6] Japanese Patent Application Publication No. 2018-188529 [Patent Document 7] Patent Publication No. 2021-028375 [Patent Document 8] Patent Publication No. 2021-028384 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a resin composition containing a polymer that is oriented even at a low heating temperature of 200°C or less and that exhibits a high retardation of retardation Re / thickness of 100 nm or more. [Means for solving the problem]

[0005] As a result of intensive research to solve the above problems, the inventors have discovered that a resin composition containing a polymer having a specific photoreactive group and a specific additive solves the above problems, promotes the thermal reorientation of the polymer at a heat treatment temperature below the heat resistance temperature of a general-purpose resin film support substrate, and makes it possible to manufacture the composition on a general-purpose resin film support substrate, thereby completing the present invention.

[0006] That is, one embodiment of the present invention is a resin composition containing 70 to 99.99 wt % of a polymer containing 1 to 50 mol % of a structural unit represented by the following formula (1) (hereinafter also referred to as "polymer represented by formula (1)"), and 0.01 to 30 wt % of a thermal reorientation promoter having a molecular weight of 200 to 10,000.

[0007] [ka]

[0008] (In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a fused aromatic ring, the ring having an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-constituting atom, and these monocyclic aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have a substituent. R 1 and R 2 may be the same or different and represent 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, and an optionally substituted aromatic group having 4 to 20 carbon atoms. X represents a group selected from the group consisting of an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. S 1 and S 2 each independently represents a spacer group or a single bond. The spacer group represents a group selected from the group consisting of a -CH2- group, a -CH2CH2- group, and an alkylene group having 3 to 20 carbon atoms, and two or more non-adjacent -CH2- groups in the alkylene group may each independently be replaced by an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. n is 0 or 1. Another aspect of the present invention relates to an optical thin film containing the resin composition.

[0009] Another aspect of the present invention relates to a retardation film including the optical thin film.

[0010] Furthermore, another aspect of the present invention relates to a liquid crystal alignment film comprising the optical thin film. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a resin composition that exhibits reactivity to ultraviolet light, an optical thin film that can be formed on a general-purpose resin substrate to exhibit high retardation even at a heat treatment temperature of 200°C or less, and a retardation film and a liquid crystal alignment film made of the thin film. DETAILED DESCRIPTION OF THE INVENTION

[0012] The resin composition according to one embodiment of the present invention will be described in detail below.

[0013] One aspect of the present invention is a resin composition containing 70 to 99.99% by weight of a polymer represented by the formula (1) and 0.01 to 30% by weight of a thermal reorientation promoter having a molecular weight of 200 to 10,000.

[0014] In formula (1), ring A, ring B, and ring C each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a fused aromatic ring, the ring having an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-constituting atom, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.

[0015] Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a tert-butyl group, a pentyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, a tert-pentyl group, a 1-methylbutyl group, a 1-ethylpropyl 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 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group.

[0016] Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a methoxymethyloxy group, an ethoxymethyloxy group, a trifluoromethyloxy group, a 2,2-difluoroethyloxy group, a 2,2,2-trifluoroethyloxy group, a 2,2,3,3-tetrafluoropropyloxy group, a 2,2,3,3,3-pentafluoropropyloxy group, and a [2,2,2-trifluoro-1-(trifluoromethyl)ethyl]oxy group.

[0017] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[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. In terms of ease of synthesis, a ring selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, and a pyridine ring is preferred, and a ring selected from the group consisting of a benzene ring and a biphenyl ring is more preferred.

[0019] In formula (1), R 1 and R 2R may be the same or different and represent 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 having 4 to 20 carbon atoms. 1 and R 2 The optionally substituted alkyl group having 1 to 20 carbon atoms, represented by the formula (I), may be linear, branched, or cyclic, and the alkyl group having 1 to 20 carbon atoms may be substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom.

[0020] Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a methoxymethyloxy group, an ethoxymethyloxy group, a trifluoromethyloxy group, a 2,2-difluoroethyloxy group, a 2,2,2-trifluoroethyloxy group, a 2,2,3,3-tetrafluoropropyloxy group, a 2,2,3,3,3-pentafluoropropyloxy group, and a [2,2,2-trifluoro-1-(trifluoromethyl)ethyl]oxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0021] Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a tert-butyl group, a pentyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, a tert-pentyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a hexyl group, a 4-methylpentyl group, a 1-methylpentyl group, a 1-ethylbutyl group, a heptyl group, an octyl group, a nonyl group, a decyl 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 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group.

[0022] R 1 and R 2Examples of the optionally substituted cycloalkyl group having 3 to 8 carbon atoms represented by the following formula include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0023] R 1 and R 2 Examples of the optionally substituted aromatic group having 4 to 20 carbon atoms represented by the formula (I) include a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and a pyridine ring.

[0024] X represents a group selected from the group consisting of an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms.

[0025] Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms.

[0026] Examples of the optionally substituted alkoxy group having 1 to 5 carbon atoms for X and Y include a methoxy group, an ethoxy group, a methoxymethyloxy group, an ethoxymethyloxy group, a trifluoromethyloxy group, a 2,2-difluoroethyloxy group, a 2,2,2-trifluoroethyloxy group, a 2,2,3,3-tetrafluoropropyloxy group, a 2,2,3,3,3-pentafluoropropyloxy group, and a [2,2,2-trifluoro-1-(trifluoromethyl)ethyl]oxy group.

[0027] Examples of the halogen atom in X and Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0028] Examples of the optionally substituted acyloxy group having 1 to 5 carbon atoms in X and Y include an acetyloxy group, a propionyloxy group, a butyryloxy group, and a valeryloxy group.

[0029] Examples of the optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms for X and Y include a methanesulfonyloxy group, an ethanesulfonyloxy group, a propanesulfonyloxy group, and a trifluoromethanesulfonyloxy group.

[0030] Examples of the optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms include a benzenesulfonyl group, a paratoluenesulfonyloxy group, and an orthonitrobenzenesulfonyl group.

[0031] Examples of the optionally substituted aryloxy group having 4 to 20 carbon atoms include a phenoxy group, a naphthyloxy group, and an anthryloxy group.

[0032] In terms of excellent photoreactivity, X and Y are preferably either a chlorine atom or a bromine atom.

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

[0034] n represents 0 or 1.

[0035] In the polymer contained in the resin composition of the present invention, in formula (1), ring A, ring B, and ring C are preferably rings selected from the group consisting of optionally substituted monocyclic aromatic rings, optionally substituted polycyclic aromatic rings, and optionally substituted fused aromatic rings, each of which has an atom selected from the group consisting of carbon atoms and nitrogen atoms as a ring-constituting atom, and R 1 and R 2 may be the same or different and are preferably groups selected from the group consisting of hydrogen atoms and optionally substituted alkyl groups having 1 to 20 carbon atoms.

[0036] The polymer represented by formula (1) has the following photoreactive structure.

[0037] [ka]

[0038] (In the formula, R 1 , A, B, X and Y are R in the formula (1), respectively. 1 , A, B, X, and Y.) Examples of the photoreactive structure include structures represented by the following formulas (2-1) to (2-18).

[0039] [ka]

[0040] (In the formulas (2-1) to (2-18), the polymer chain may form an ether bond, which may be replaced with an amide bond, an imide bond, a urethane bond, an ester bond, or the like.) The polymer represented by formula (1) has the photoreactive structure and a structure derived from one or more compounds arbitrarily selected from the group consisting of dicarboxylic acids, dicarboxylic acid dichlorides, diamines, tetracarboxylic acid dianhydrides, polyvalent hydroxy compounds, and isocyanate compounds.

[0041] Examples of dicarboxylic acids include aliphatic dicarboxylic acids (specifically, saturated dicarboxylic acids having 2 to 20 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid, and unsaturated dicarboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, and itaconic acid), alicyclic dicarboxylic acids (cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, and the like), and aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-oxybis(benzoic acid), and 2,5-furandicarboxylic acid, and the like).

[0042] Examples of dicarboxylic acid dichlorides include saturated carboxylic acid dichlorides having 2 to 20 carbon atoms, such as oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, and sebacic acid dichloride; unsaturated dicarboxylic 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-furandicarboxylic acid dichloride.

[0043] 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, 4-amino Examples of the alkyl esters 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.

[0044] Examples of tetracarboxylic dianhydrides include pyromellitic anhydride, dibromopyromellitic dianhydride, 3,4'-biphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, octahydrobiphenylene-4a,8b:4b,8a-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-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, 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'-(ethyne-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] Oct-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 of suitable diphthalic anhydrides include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-biphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride.

[0045] Examples of polyhydric 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, cyclopentanediol, and the like. Tandanediol, cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydroquinone, tetramethylhydroquinone, 4,4'-dihydroxybiphenyl, benzenedimethanol, vanillyl alcohol, furandiethanol, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-(1,3-dimethylbutylidene)diphenol, 6,6'-dihydroxy-4,4,4',4',7,7'-hexamethyl-2,2'-spirobiphenyl Chroman, tricyclodecane dimethanol, 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 suitable hydroxy compounds include divalent hydroxy compounds such as 2,2'-dihydroxybenzophenone, 2,2'-bis(hydroxymethyl)diphenyl ether, 7,7'-dihydroxy-4,4,4',4'-tetramethyl-2,2'-spirobichroman, 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 glycols of various molecular weights; trivalent hydroxy compounds such as glycerin, trimethylolpropane, triethanolamine, 2,3,4,4'-tetrahydroxybenzophenone, 1,2,3-butanetriol, and 2,6-bis(hydroxymethyl)-4-methylphenol; and tetravalent hydroxy compounds such as pentaerythritol. Other polyvalent hydroxy compounds include various sugars.

[0046] The isocyanate compound is not particularly limited, and examples thereof include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds (monocyclic alicyclic isocyanate compounds, crosslinked cyclic alicyclic isocyanate compounds), and polyisocyanate derivatives thereof.

[0047] Examples of aromatic isocyanate compounds include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or a mixture thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate, or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate, Examples of the isocyanate include 1,3- or 1,4-tetramethylxylylene diisocyanate, or a mixture thereof (TMXDI), ω,ω'-diisocyanato-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate, or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0048] Examples of the aliphatic isocyanate compound 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 methylcaprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate.

[0049] 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-isocyanatomethyl-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 of suitable diisocyanates include methyl cyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, trans cyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI).

[0050] Examples of the crosslinked cyclic alicyclic isocyanate compound include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane.

[0051] In terms of ease of availability, it is preferable that the compound has a structure derived from at least one of a dicarboxylic acid dichloride and a polyvalent hydroxy compound.

[0052] The resin composition of the present invention is preferably used as a resin composition obtained by subjecting it to a light irradiation treatment, and since the light irradiation treatment causes retardation, it can be suitably used as an optical member.

[0053] An example of a polymer obtained by subjecting a resin composition to light irradiation treatment is a polymer containing a structure represented by the following formula (1').

[0054] [ka]

[0055] (In the formula, R 1 , R 2 , A, B, C, Y, S 1 , S 2 and n are R in the formula (1), respectively. 1 , R 2 , A, B, C, Y, S 1 , S 2 and n.) When the polymer represented by formula (1) is irradiated with polarized light, among the structural units represented by formula (1) present in the polymer, those represented by formula (1) that are oriented in the same direction as the irradiated polarized light selectively absorb light and react, thereby partially producing structural units represented by formula (1'). The polymer chains other than the structural units represented by formula (1') are thermally oriented to avoid this.

[0056] A reference (J. Chem. Soc., Chem. Commun., 1973, 647-648) discloses a compound exhibiting photo-condensed rings. The compound represented by formula (1) contained in the resin composition of the present application is synthesized from a monomer having a structure different from that of the compound disclosed in the reference.

[0057] The resin composition of the present invention contains a polymer containing a structural unit represented by formula (1) and a thermal reorientation promoter. The molecular mobility of optical thin films and retardation films obtained using the resin composition of the present invention is improved by the thermal reorientation promoter, making it possible to thermally reorient the polymer even on general-purpose resin support substrates with low heat resistance. Specifically, the novelty of this application lies in the discovery that blending a polymer containing a structural unit represented by formula (1) with a thermal reorientation promoter reduces the heating temperature required for alignment treatment. This phenomenon results in an increased birefringence at a lower heat treatment temperature compared to when the thermal reorientation promoter is not blended.

[0058] The method for producing the polymer represented by formula (1) contained in the resin composition of the present invention will be described below.

[0059] The method for producing the polymer represented by formula (1) contained in the resin composition of the present invention is not particularly limited, and it may be produced by a polymerization method known in the art, such as a solution polymerization method or a melt polymerization method.

[0060] The polymer represented by formula (1) contained in the resin composition of the present invention can be produced by copolymerizing a monomer represented by the following formula (2).

[0061] [ka]

[0062] (In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a fused aromatic ring, the ring having an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-constituting atom, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have a substituent. R 1 and R 2 may be the same or different and represent 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, and an optionally substituted aromatic group having 4 to 20 carbon atoms. X represents a group selected from the group consisting of an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. F 1 and F 2 each independently represents a group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, or an isocyanato group; and n represents 0 or 1. In formula (2), ring A, ring B, and ring C each independently represent a ring selected from the group consisting of an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, whose ring-constituting atom is 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 a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.

[0063] In formula (2), 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. In terms of ease of synthesis, a ring selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, and a pyridine ring is preferred, and a ring selected from the group consisting of a benzene ring and a biphenyl ring is more preferred.

[0064] In formula (2), R 1 and R 2 may be the same or different and represent 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, and an optionally substituted aromatic group having 4 to 20 carbon atoms.

[0065] R 1 and R 2 The optionally substituted alkyl group having 1 to 20 carbon atoms, represented by the formula (I), may be linear, branched, or cyclic, and the alkyl group having 1 to 20 carbon atoms may be substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom.

[0066] 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 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group.

[0067] R 1 and R 2 Examples of the optionally substituted cycloalkyl group having 3 to 8 carbon atoms represented by the following formula include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0068] R 1 and R 2 Examples of the optionally substituted aromatic group having 4 to 20 carbon atoms represented by the formula (I) include a phenyl group, a naphthyl group, and a biphenylyl group.

[0069] X represents a group selected from the group consisting of an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. X is preferably either a chlorine atom or a bromine atom, as this provides excellent photoreactivity.

[0070] Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms.

[0071] Examples of the optionally substituted alkoxy group having 1 to 5 carbon atoms, represented by X and Y, include a methoxy group, an ethoxy group, a methoxymethyloxy group, an ethoxymethyloxy group, a trifluoromethyloxy group, a 2,2-difluoroethyloxy group, a 2,2,2-trifluoroethyloxy group, a 2,2,3,3-tetrafluoropropyloxy group, a 2,2,3,3,3-pentafluoropropyloxy group, and a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group.

[0072] Examples of halogen atoms represented by X and Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0073] Examples of optionally substituted acyloxy groups having 1 to 5 carbon atoms represented by X and Y include an acetyloxy group, a propionyloxy group, a butyryloxy group, and a valeryloxy group.

[0074] Examples of optionally substituted alkylsulfonyloxy groups having 1 to 5 carbon atoms, represented by X and Y, include alkylsulfonyloxy groups having 1 to 5 carbon atoms which may be substituted with fluorine, and more specific examples include a methanesulfonyloxy group, an ethanesulfonyloxy group, a propanesulfonyloxy group, and a trifluoromethanesulfonyloxy group.

[0075] Examples of optionally substituted arylsulfonyloxy groups having 6 to 11 carbon atoms, represented by X and Y, include a benzenesulfonyloxy group, a paratoluenesulfonyloxy group, and an orthonitrobenzenesulfonyloxy group.

[0076] Examples of the optionally substituted aryloxy group having 4 to 20 carbon atoms represented by X and Y include a phenoxy group, a naphthyloxy group, and an anthryloxy group.

[0077] In formula (2), F 1 and F 2 each independently represents a group selected from the group consisting of a hydroxy group, an amino group, a carboxy group, and an isocyanato group. From the viewpoint of availability, a hydroxy group is preferred.

[0078] n represents 0 or 1.

[0079] In terms of having liquid crystal properties, ring A, ring B, and ring C in formula (2) are preferably rings selected from the group consisting of optionally substituted monocyclic aromatic rings, optionally substituted polycyclic aromatic rings, and optionally substituted fused aromatic rings, each of which has an atom selected from the group consisting of carbon atoms and nitrogen atoms as a ring-constituting atom. 1 and R 2 is preferably a group selected from the group consisting of a hydrogen atom and an optionally substituted alkyl group having 1 to 20 carbon atoms, in terms of having liquid crystallinity. This results in a polymer having liquid crystallinity.

[0080] The monomer represented by the formula (2) is preferably a compound represented by the following formula (2-1).

[0081] [ka]

[0082] (In the formula, R 1 , A, B, X, Y, F 1 and F 2 are R in the above formula (3), 1 , A, B, X, Y, F 1 and F 2 is equivalent to The monomer represented by the formula (2) is particularly preferably any one of the following formulas (2-1-1) to (2-1-9) and (2-2-1) among the formula (2-1).

[0083] [ka]

[0084] (In the formula, R 1 and R 2 are R in the above formula (2), 1 and R 2 is synonymous with. X arepresents a group selected from the group consisting of a halogen atom, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, and 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 independently represents a hydroxy group or an amino group. The monomer represented by the formula (2) is particularly preferably any one of the following formulas (2-1-1-1) to (2-2-1-3) among the formula (2-1-1).

[0085] [ka]

[0086] (In the formula, R 1 and R 2 are R in the above formula (2), 1 and R 2 is equivalent to The polymer represented by formula (1) contained in the resin composition of the present invention is synthesized by copolymerizing the monomer represented by formula (2) with at least one copolymerizable monomer arbitrarily selected from the group consisting of dicarboxylic acids, dicarboxylic acid dichlorides, diamines, tetracarboxylic acid dianhydrides, polyvalent hydroxy compounds, and isocyanate compounds. Preferably, the polymer represented by formula (1) is synthesized by copolymerizing the monomer represented by formula (2) with at least one copolymerizable monomer selected from the group consisting of dicarboxylic acid dichlorides and polyvalent hydroxy compounds, particularly preferably dicarboxylic acid chlorides.

[0087] When copolymerizing, for example, by a solution polymerization method to produce the polymer represented by formula (1) contained in the resin composition of the present invention, the polymer can be easily obtained by polymerizing the monomer represented by formula (2) and a dicarboxylic acid dichloride in an aqueous or organic solvent system under basic conditions.

[0088] The monomer to be copolymerized with the monomer represented by formula (2) is not particularly limited as long as it is a compound that forms a polymer together with the monomer represented by formula (2), and dicarboxylic acids, dicarboxylic acid dichlorides, polyvalent hydroxy compounds, diamines, tetracarboxylic acid dianhydrides, and diisocyanates can be used. Among these, dicarboxylic acid dichlorides or polyvalent hydroxy compounds are preferred, and dicarboxylic acid chlorides are particularly preferred.

[0089] The dicarboxylic acid used in producing the polymer represented by formula (1) contained in the resin composition of the present invention can be selected from known dicarboxylic acids without any limitation.

[0090] Examples of dicarboxylic acids include aliphatic dicarboxylic acids (specifically, saturated dicarboxylic acids having 2 to 20 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid, and unsaturated dicarboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, and itaconic acid), alicyclic dicarboxylic acids (cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, and the like), and aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-oxybis(benzoic acid), 2,5-furandicarboxylic acid, and the like).

[0091] The dicarboxylic acid dichloride used in producing the polymer represented by formula (1) contained in the resin composition of the present invention can be selected from known dicarboxylic acid dichlorides without any limitation.

[0092] Examples of dicarboxylic acid dichlorides include saturated carboxylic acid dichlorides having 2 to 20 carbon atoms, such as oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, and sebacic acid dichloride; unsaturated dicarboxylic 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-furandicarboxylic acid dichloride.

[0093] The polyvalent hydroxy compound used in producing the polymer represented by formula (1) contained in the resin composition of the present invention can be selected without limitation from known polyvalent hydroxy compounds.

[0094] Examples of polyhydric 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, cyclopentanediol, and the like. Tandanediol, cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydroquinone, tetramethylhydroquinone, 4,4'-dihydroxybiphenyl, benzenedimethanol, vanillyl alcohol, furandiethanol, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-(1,3-dimethylbutylidene)diphenol, 6,6'-dihydroxy-4,4,4',4',7,7'-hexamethyl-2,2'-spirobiphenyl Chroman, tricyclodecane dimethanol, 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 suitable hydroxy compounds include divalent hydroxy compounds such as 2,2'-dihydroxybenzophenone, 2,2'-bis(hydroxymethyl)diphenyl ether, 7,7'-dihydroxy-4,4,4',4'-tetramethyl-2,2'-spirobichroman, 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 glycols of various molecular weights; trivalent hydroxy compounds such as glycerin, trimethylolpropane, triethanolamine, 2,3,4,4'-tetrahydroxybenzophenone, 1,2,3-butanetriol, and 2,6-bis(hydroxymethyl)-4-methylphenol; and tetravalent hydroxy compounds such as pentaerythritol. Other polyvalent hydroxy compounds include various sugars.

[0095] The diamine used in producing the polymer represented by formula (1) contained in the resin composition of the present invention can be selected from known diamines without any limitation.

[0096] 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, 4-amino Examples of the alkyl esters 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.

[0097] The tetracarboxylic dianhydride used to produce the polymer represented by formula (1) contained in the resin composition of the present invention can be selected from known tetracarboxylic dianhydrides without any limitation.

[0098] Examples of tetracarboxylic dianhydrides include pyromellitic anhydride, dibromopyromellitic dianhydride, 3,4'-biphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, octahydrobiphenylene-4a,8b:4b,8a-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-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, 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'-(ethyne-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] Oct-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 of suitable diphthalic anhydrides include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-biphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride.

[0099] The diisocyanate used in producing the polymer represented by formula (1) contained in the resin composition of the present invention can be selected from known diisocyanates without any limitation.

[0100] The isocyanate compound used in producing the polymer represented by formula (1) contained in the resin composition of the present invention is not particularly limited, and examples thereof include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds (monocyclic alicyclic isocyanate compounds, crosslinked cyclic alicyclic isocyanate compounds), and polyisocyanate derivatives thereof.

[0101] Examples of aromatic isocyanate compounds include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or a mixture thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate, or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate, Examples of the isocyanate include 1,3- or 1,4-tetramethylxylylene diisocyanate, or a mixture thereof (TMXDI), ω,ω'-diisocyanato-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4-, or 1,8-naphthalene diisocyanate, or a mixture thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0102] Examples of the aliphatic isocyanate compound 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 methylcaprate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and decamethylene diisocyanate.

[0103] 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-isocyanatomethyl-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 of suitable diisocyanates include methyl cyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, trans cyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI).

[0104] Examples of the crosslinked cyclic alicyclic isocyanate compound include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanatomethyl bicycloheptane, and di(diisocyanatomethyl)tricyclodecane.

[0105] The solvent used in producing the polymer represented by formula (1) contained in the resin composition of the present invention can be any solvent that does not harm the reaction, and examples thereof include ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, dimethoxyethane, tetrahydrofuran (THF), and dioxane; nitrile solvents such as acetonitrile and propionitrile; aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; amide solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; halogenated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone; acetic acid, dimethyl sulfoxide (DMSO), and water. These solvents may be used alone or in combination of two or more in any ratio.

[0106] When the polymer represented by formula (1) contained in the resin composition of the present invention is subjected to interfacial polymerization in a two-phase system of water-organic solvent, a phase transfer catalyst may be used to promote the reaction. Examples of the phase transfer catalyst 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; and 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.

[0107] When the polymer represented by formula (1) contained in the resin composition of the present invention is subjected to interfacial polymerization in a two-phase system of water and an organic solvent, it is desirable to use a base to promote the reaction. Examples of the base 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.

[0108] The resin composition of the present invention contains a thermal reorientation promoter. The molecular mobility of the optical thin film and retardation film obtained using the resin composition of the present invention is improved by the thermal reorientation promoter, making it possible to perform a thermal reorientation treatment of the polymer even on a general-purpose resin support substrate with a low heat resistance temperature.

[0109] The thermal reorientation promoter contained in the resin composition of the present invention has a molecular weight of 200 to 10,000. If the molecular weight is less than 200, problems of precipitation and exudation of the thermal reorientation promoter or volatilization of the thermal reorientation promoter occur in high-temperature environments, and the performance cannot be maintained when the resin composition is made into an optical thin film. If the molecular weight is more than 10,000, the efficiency of improving the molecular orientation of polyester is low. The thermal reorientation promoter of the present invention preferably has a molecular weight of 300 to 10,000 due to its low volatility during heat treatment.

[0110] The blend ratio of the polymer represented by formula (1) and the thermal reorientation promoter in the resin composition of the present invention is 70 to 99.99 wt% of the polymer represented by formula (1) and 0.01 to 30 wt% of the thermal reorientation promoter. To address the issue of precipitation and exudation of the thermal reorientation promoter in high-temperature environments, a more preferred blend ratio is 85 to 99.9 wt% of the polymer represented by formula (1) and 0.1 to 15 wt% of the thermal reorientation promoter. From the perspective of thermal reorientation promotion efficiency, a particularly preferred blend ratio is 85 to 99.0 wt% of the polymer represented by formula (1) and 1.0 to 15 wt% of the thermal reorientation promoter. In the present invention, when the ratio of the thermal reorientation promoter is less than 0.01 wt%, it becomes difficult to promote thermal reorientation, and when it is more than 30 wt%, precipitation and exudation of the thermal reorientation promoter are likely to occur.

[0111] Examples of the thermal reorientation promoter of the present invention include plasticizers, antioxidants, and light stabilizers.

[0112] Examples of the plasticizer include carboxylic acid esters, phosphoric acid esters, and polymer-based plasticizers.

[0113] Specific examples of carboxylic acid esters include phthalates, trimellitates, pyromellitates, citrates, oleates, ricinoleates, sebacates, stearates, adipates, and epoxidized esters. Among these, phthalates are preferred because of their easy availability.

[0114] Examples of phthalate esters include those containing a structure represented by the following formula (3) and having a molecular weight of 200 to 10,000.

[0115] [ka]

[0116] (In formula (3), R 3 and R 4 each independently represents one selected from the group consisting of an optionally substituted alkyl group, aromatic group, heterocyclic group, polycyclic aromatic group, and fused-ring aromatic group each having 1 to 20 carbon atoms, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 3 and R 4 and each independently preferably have 2 to 20 carbon atoms.) Specific examples of phthalate esters include diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, dihexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, di-n-decyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, di-2-ethylhexyl phthalate, benzyl butyl phthalate, and di-2-ethylhexyl isophthalate.

[0117] Examples of trimellitic acid esters include those containing a structure represented by the following formula (4) and having a molecular weight of 200 to 10,000.

[0118] [ka]

[0119] (In formula (4), R 5 , R6 and R 7 each independently represents one selected from the group consisting of an optionally substituted alkyl group, aromatic group, heterocyclic group, polycyclic aromatic group, and fused-ring aromatic group, each having 1 to 20 carbon atoms, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of trimellitic acid esters include tributyl trimellitate, tris(2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, tri-n-decyl trimellitate, triisodecyl trimellitate, triundecyl trimellitate, tridodecyl trimellitate, tri(tridecyl) trimellitate, and tritetradecyl trimellitate.

[0120] Examples of pyromellitic acid esters include those containing a structure represented by the following formula (5) and having a molecular weight of 200 to 10,000.

[0121] [ka]

[0122] (In formula (5), R 8 , R 9 , R 10 and R 11 each independently represents one selected from the group consisting of an optionally substituted alkyl group, aromatic group, heterocyclic group, polycyclic aromatic group, and fused-ring aromatic group, each having 1 to 20 carbon atoms, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of pyromellitic acid esters include 2-ethylhexyl pyromellitic acid ester, tetra(2-ethylhexyl) pyromellitic acid, tetra-n-octyl pyromellitic acid, tetraisooctyl pyromellitic acid, tetranonyl pyromellitic acid, tetraisononyl pyromellitic acid, tetra-n-decyl pyromellitic acid, tetraisodecyl pyromellitic acid, tetraundecyl pyromellitic acid, tetradodecyl pyromellitic acid, tetratridecyl pyromellitic acid, and tetra(tetradecyl) pyromellitic acid.

[0123] Examples of citrate esters include those containing a structure represented by the following formula (6) and having a molecular weight of 200 to 10,000.

[0124] [ka]

[0125] (In formula (6), R 12 , R 13 , and R 14 R each independently represents one selected from the group consisting of an optionally substituted alkyl group, aromatic ring, heterocyclic group, polycyclic aromatic group, or fused-ring aromatic group having 1 to 20 carbon atoms, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 15 represents one selected from the group consisting of a hydrogen atom, an optionally substituted acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aromatic group, a heterocyclic group, a polycyclic aromatic group, and a fused-ring aromatic group, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of citrate esters include trimethyl citrate, triethyl citrate, tripropyl citrate, tributyl citrate, tripentyl citrate, trihexyl citrate, trimethyl acetylcitrate, triethyl acetylcitrate, tripropyl acetylcitrate, tributyl acetylcitrate, tripentyl acetylcitrate, and trihexyl acetylcitrate.

[0126] Examples of oleic acid esters include those containing a structure represented by the following formula (7) and having a molecular weight of 200 to 10,000.

[0127] [ka]

[0128] (In formula (7), R 16 represents one member selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of oleate esters include methyl oleate, ethyl oleate, propyl oleate, butyl oleate, hexyl oleate, heptyl oleate, n-octyl oleate, nonyl oleate, and n-decyl oleate.

[0129] Examples of ricinoleic acid esters include those containing a structure represented by the following formula (8) and having a molecular weight of 200 to 10,000.

[0130] [ka]

[0131] (In formula (8), R 17represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 18 represents one member selected from the group consisting of a hydrogen atom, an optionally substituted acetyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of ricinoleic acid esters include methyl ricinoleate, ethyl ricinoleate, propyl ricinoleate, butyl ricinoleate, pentyl ricinoleate, hexyl ricinoleate, methyl acetylricinoleate, ethyl acetylricinoleate, and propyl acetylricinoleate.

[0132] Examples of sebacate esters include those containing a structure represented by the following formula (9) and having a molecular weight of 200 to 10,000.

[0133] [ka]

[0134] (In formula (9), R 19 and R 20 each independently represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of sebacate esters include dimethyl sebacate, diethyl sebacate, dipropyl sebacate, dibutyl sebacate, di(2-ethylhexyl) sebacate, di-n-octyl sebacate, diisooctyl sebacate, dinonyl sebacate, diisononyl sebacate, di-n-decyl sebacate, diisodecyl sebacate, diundecyl sebacate, didodecyl sebacate, ditridecyl sebacate, and ditetradecyl sebacate.

[0135] Examples of stearic acid esters include those containing a structure represented by the following formula (10) and having a molecular weight of 200 to 10,000.

[0136] [ka]

[0137] (In formula (10), R 21 represents one member selected from the group consisting of an optionally substituted alkyl group having 1 to 40 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of stearic acid esters include methyl stearate, ethyl stearate, propyl stearate, butyl stearate, pentyl stearate, hexyl stearate, heptyl stearate, n-octyl stearate, nonyl stearate, decyl stearate, dodecyl stearate, phenyl stearate, glycidyl stearate, methyl dichlorostearate, monostearin, and tristearin.

[0138] Examples of adipic acid esters include those containing a structure represented by the following formula (11) and having a molecular weight of 200 to 10,000.

[0139] [ka]

[0140] (In formula (11), R 22 and R 23 each independently represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 22 and R 23 and each independently preferably have 2 to 20 carbon atoms.) Specific examples of adipate esters include dibutyl adipate, diisobutyl adipate, bis[2-(2-butoxyethoxy)ethyl] adipate, di(2-ethylhexyl) adipate, di-n-octyl adipate, diisooctyl adipate, dinonyl adipate, diisononyl adipate, di-n-decyl adipate, diisodecyl adipate, diundecyl adipate, didodecyl adipate, ditridecyl adipate, and ditetradecyl adipate.

[0141] The epoxidized ester is not particularly limited as long as it has a molecular weight of 200 or more and has one or more epoxy groups and ester bonds, and examples thereof include 4,5-epoxycyclohexane-1,2-dicarboxylate di(2-ethylhexyl), 4,5-epoxycyclohexane-1,2-dicarboxylate di(9,10-epoxystearyl), epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid isobutyl, and epoxidized fatty acid 2-ethylhexyl.

[0142] The phosphate ester may include a compound represented by the following formula (12).

[0143] [ka]

[0144] (In formula (12), R 24 ~R 26 each independently represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 24 ~R 26 and each independently preferably have 3 to 20 carbon atoms.) Specific examples of phosphate esters include tributyl phosphate, triamyl phosphate, trihexyl phosphate, triheptyl phosphate, tri-n-octyl phosphate, trinonyl phosphate, tri-n-decyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-butoxyethyl) phosphate, tris(2-chloroethyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, 2-ethylhexyldiphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, tris(2-ethylhexyl) phosphate, and tricresyl phosphate.

[0145] Specific examples of polymer-based plasticizers include polyester-based plasticizers and polyether-based plasticizers.

[0146] The polyester plasticizer is a polymer containing a structural unit represented by the following formula (13), and examples thereof include those having a molecular weight of 200 to 10,000.

[0147] [ka]

[0148] (In formula (13), R 27 and R 28each independently represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of polyester plasticizers include Adeka Cizer PN-160, PN-9302, PN-150, PN-170, PN-7230, PN-1010, PN-1020, P-200, PN-650, PN-7650, PN-1030, PN-1430, HPN-3130, PN-400, P-5040, PN-7250, PN-250, PN-7220, PN-7550, PN-446, and PN-31 0, P-300, PN-280, PN-5090 (all trade names, manufactured by ADEKA Corporation), D620, D623, D643, D645, D633, D620N, D623N, D643D, D640A, D671N (all trade names, manufactured by Mitsubishi Chemical Corporation), Polycizer W-230-H, W-1430-EL, W-2050, W-2310 (all trade names, manufactured by DIC Corporation), and the like.

[0149] The polyether plasticizer is a polymer containing a structural unit represented by the following formula (14), and examples thereof include those having a molecular weight of 200 to 10,000.

[0150] [ka]

[0151] (In formula (14), R 29 represents one member selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of polyether-based plasticizers include Adeka Cizer RS-107, RS-700, RS-735, RS-966, and RS-1000 (all trade names, manufactured by ADEKA CORPORATION), and Monocizer W-260 and W-262 (all trade names, manufactured by DIC Corporation).

[0152] Examples of antioxidants include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, lactone-based antioxidants, hydroxylamine-based antioxidants, and vitamin E-based antioxidants. Examples of phenol-based antioxidants include those containing a structure represented by the following formula (15) and having a molecular weight of 200 to 10,000.

[0153] [ka]

[0154] (In formula (15), R 30 , R 34 at least one of the groups represents one selected from the group consisting of an optionally substituted secondary alkyl group having 3 to 20 carbon atoms, a tertiary alkyl group having 4 to 20 carbon atoms, a thioether group having 6 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, an -(C=O)O- group, an -O(C=O)- group, an -O(C=O)-O- group, an -C(=O)-NH- group, an -NH-(C=O)- group, an -CH=CH- group, or an -C≡C- group. and the other represents one selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a thioether group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. These structures are not particularly limited, but a tert-butyl group is preferred from the viewpoint of availability. 31 ~R 33each independently represents one selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of phenolic antioxidants include Irganox 245 (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]), Irganox 1010 (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), Irganox 1035 (2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), Irganox 1076 (octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), Irganox 1098 (N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide]), and Irganox 1135 (Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate), Irganox 1330 (2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene), Irganox 1520 (2,4-bis(octylthiomethyl)-6-methylphenol), Irganox 259 (1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), Irganox 3114 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione), Irganox 565 (4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol) (all trade names, manufactured by BASF Japan Ltd.).

[0155] The phenolic antioxidant may have a molecular weight of 200 to 10,000, and is not limited to those represented by formula (15). Examples include galvinoxyl free radical, 3,3',5,5'-tetra-tert-butyl-4,4'-stilbenequinone, and 4-(hexyloxy)-2,3,6-trimethylphenol.

[0156] Examples of the amine-based antioxidant that can be used as the thermal reorientation promoter of the present invention include those having a molecular weight of 200 to 10,000 and containing a structure represented by the following formula (16).

[0157] [ka]

[0158] (In formula (16), R 34 represents a ring selected from the group consisting of an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, the ring of which is composed of an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and these aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have a substituent. 35 represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 35 preferably has 9 to 20 carbon atoms.) Specific examples of the amine antioxidant represented by formula (16) include 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-1-naphthylamine, N,N'-di-sec-butyl-1,4-phenylenediamine, 4-isopropylaminodiphenylamine, N,N'-diphenyl-1,4-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-N,N'-phenylenediamine, N,N'-di-2-naphthyl-1,4-phenylenediamine, and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine.

[0159] The amine antioxidant may have a molecular weight of 200 to 10,000, and is not limited to those represented by formula (16). Examples include 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and poly(2,2,4-trimethyl-1,2-dihydroquinoline).

[0160] Examples of phosphorus-based antioxidants include those containing a structure represented by the following formula (17) and having a molecular weight of 200 to 10,000.

[0161] [ka]

[0162] (In formula (17), R 36 and R 37 R each independently represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 38represents one selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 36 , R 37 and R 38 and each independently preferably have 3 to 20 carbon atoms.) Specific examples of phosphorus-based antioxidants include tributyl phosphite, triphenyl phosphite, trihexyl phosphite, tri-o-cresyl phosphite, tri-m-cresyl phosphite, tri-p-cresyl phosphite, tris(2-ethylhexyl) phosphite, trioctyl phosphite, triisodecyl phosphite, tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tris(2,4-di-tert-butylphenyl) phosphite, and trioleyl phosphite.

[0163] Examples of sulfur-based antioxidants include those containing a structure represented by the following formula (18) and having a molecular weight of 200 to 10,000.

[0164] [ka]

[0165] (In formula (18), R 39 represents one member selected from the group consisting of an optionally substituted alkyl group having 1 to 20 carbon atoms, a heterocycle, an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 40represents one member selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, and a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. 39 and R 40 and each independently preferably have 6 to 20 carbon atoms.) Specific examples of sulfur-based antioxidants include didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, and pentaerythritol tetrakis[3-(dodecylthio)propionate].

[0166] Examples of the light stabilizer include hindered amine light stabilizers.

[0167] Examples of hindered amine light stabilizers include those having a molecular weight of 200 to 10,000 and having a structural unit represented by the following formula (19).

[0168] [ka]

[0169] (In formula (19), S 3 -O-, -CO-, -NR 41 -, where R 41 represents a hydrogen atom or a group consisting of an optionally substituted alkyl group having 1 to 5 carbon atoms. 42 ~R 45are each independently one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a heterocycle, an aromatic ring, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Among these, a methyl group is particularly preferred from the viewpoint of availability. R 46 represents one member selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aromatic ring, a heterocycle, a polycyclic aromatic ring, or a fused aromatic ring, which may have a bond such as an -O- group, a -(C=O)O- group, a -O(C=O)- group, a -O(C=O)-O- group, a -C(=O)-NH- group, a -NH-(C=O)- group, a -CH=CH- group, or a -C≡C- group. Specific examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)isophthalamide, and sebaceous acid stabilizers. Examples thereof include bis(2,2,6,6-tetramethyl-4-piperidyl) malonate, bis(2,2,6,6-tetramethyl-4-piperidyl-1-oxyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl) butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0170] Among these thermal reorientation promoters, plasticizers are preferred because they are easily available, have good compatibility with polymers, and have particularly excellent thermal reorientation promoting properties even after being incorporated into the polymer.

[0171] The resin composition of the present invention may contain at least one surfactant to reduce unevenness in the thickness of the resulting thin film. Examples of surfactants that can be contained include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkylethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, and fluoroalkyl ammonium salts, with fluorine-containing surfactants being particularly preferred.

[0172] The resin composition of the present invention may contain other polymers, polymer electrolytes, conductive complexes, pigments, dyes, antistatic agents, antiblocking agents, lubricants, etc., within the scope of the invention.

[0173] The resin composition of the present invention can be obtained by blending a polymer having a photoreactive group and represented by formula (1) with a thermal reorientation promoter (hereinafter referred to as a polymer or the like).

[0174] Blending methods that can be used include melt blending and solution blending. Melt blending involves melting and kneading polymers and other components by heating. Solution blending involves dissolving and blending polymers and other components in a solvent. Examples of solvents that can be used in solution blending include halogenated solvents such as 1,1,1,3,3,3-hexafluoroisopropanol, methylene chloride, and chloroform; aromatic solvents such as toluene and xylene; ketone solvents such as cyclopentanone, acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcoholic solvents such as methanol, ethanol, and propanol; ether solvents such as dioxane and tetrahydrofuran; and dimethylformamide and N-methylpyrrolidone. Polymers and other components can be dissolved in a solvent and then blended. Alternatively, powders or pellets of each polymer can be kneaded and then dissolved in a solvent. The resulting blend polymer solution can be poured into a poor solvent to precipitate a resin composition, or the blend polymer solution itself can be used to produce an optical thin film.

[0175] The resin composition of the present invention can be used in the form of a thin film. There are no particular limitations on the method for producing the thin film, and examples thereof include a melt film-forming method and a solution casting method.

[0176] <Melt film forming method> Specific examples of the melt film-forming method include melt extrusion using a T-die, calendar molding, heat pressing, co-extrusion, co-melting, multi-layer extrusion, and inflation molding, and are not particularly limited.

[0177] <Solution casting method> The solution casting method is a method in which a solution (hereinafter referred to as "casting dope") in which a polymer is dissolved in a solvent is cast onto a support substrate, and the solvent is then removed by heating or other methods to obtain a thin film. Methods for casting the casting dope onto the support substrate include spin coating, T-die coating, doctor blade coating, bar coating, roll coating, and lip coating. The most common industrial method is to continuously extrude the casting dope from a die onto a belt- or drum-shaped support substrate. Examples of support substrates that can be used include glass substrates, metal substrates such as stainless steel and ferrotype substrates, and films such as polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, and polyimide.

[0178] A thin film made of the resin composition of the present invention exhibits retardation when irradiated with light. Examples of the light to be irradiated include ultraviolet light, particularly polarized ultraviolet light or obliquely incident ultraviolet light. When ultraviolet light is used, the wavelength of the ultraviolet light is appropriately selected from the range of 200 to 400 nm. The amount of irradiation energy is 10 to 10,000 mJ / cm. 2 It is preferable that:

[0179] After the light irradiation, the thin film made of the resin composition of the present invention can be further subjected to a heat treatment to impart optical properties. This process allows the thin film made of the resin composition of the present invention to exhibit retardation. The heat treatment temperature can be, for example, in the range of 50 to 400°C, and from the viewpoint of the heat resistance of the substrate, the heat treatment temperature is preferably in the range of 50 to 200°C.

[0180] The thin film of the present invention has a retardation (Re) of 100 nm or more, calculated based on a film thickness of 10 μm and expressed by the following mathematical formula (A) as measured using a 589 nm light source.

[0181] Re=(ny-nx)×d (A) (In formula (A), nx represents the refractive index in the in-plane fast axis direction, ny represents the refractive index in the in-plane slow axis direction, and d represents the film thickness (nm).) In the thin film of the present invention after light irradiation, it is preferable that a retardation of Re>100 nm or more is exhibited by a heating and baking treatment at 200° C. or less after light irradiation.

[0182] As described above, the thin film of the present invention can be suitably used as an optical thin film, and in particular, since it exhibits retardation, it can be suitably used as a retardation film.

[0183] When the thin film of the present invention is used as a retardation film, it may be used as a single film or as a multi-layer film laminated with other films.

[0184] The thin film of the present invention has excellent liquid crystal alignment properties and can therefore be suitably used as a component of a liquid crystal alignment film. [Example]

[0185] The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to these examples.

[0186] <Polarized UV irradiation> An ultra-high pressure mercury lamp light source (manufactured by Asahi Spectroscopy, product name: REX-250) incorporating a bandpass filter (313 nm) was used, and only P-polarized light was extracted using a polarizing beam splitter of the corresponding wavelength and used for irradiation.

[0187] <Heat treatment> Heat treatment was carried out using a non-oxidizing atmosphere inert oven (manufactured by ESPEC, product name: IPHH-202).

[0188] <Measurement of phase difference characteristics> The retardation properties of the retardation film were measured using a sample tilting automatic birefringence meter (manufactured by AXOMETRICS, trade name: AxoScan) with light having a wavelength of 589 nm.

[0189] <Thin film thickness measurement> The thickness of the thin film was measured using a spectroscopic ellipsometer (manufactured by JA Woollam, trade name: RC2-U).

[0190] <Polarizing microscope observation> The low molecular weight liquid crystal on the thin film was observed using a microscope (Olympus, product name: BX53), a polarizing condenser-polarizer (Olympus, product name: U-POC-2), and an analyzer (Olympus, product name: U-AN360P-2), and the liquid crystal orientation was observed.

[0191] <Synthesis Example 1> 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 that, the volatiles were removed under reduced pressure, and THF (8 mL) was added to the resulting residue. This solution was used in its entirety in the next reaction.

[0192] 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 and, with stirring, sodium bicarbonate (1.05 g, 12.6 mmol) was added, followed by the dropwise addition of the previously prepared THF solution of the acid chloride over 5 minutes. The mixture was allowed to warm to room temperature, stirred vigorously for 4 hours, and then concentrated under reduced pressure. The resulting solid was collected by filtration and washed with water (50 mL) and hexane:ethyl acetate (75:25) (50 mL) to give 2-chloro-4-methoxy-N-{4'-methoxy(1,1'-biphenyl)-4-yl}benzamide as a light brown solid (yield: 1.68 g, 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 (0.960 g, 2.61 mmol) in DMF (7 mL) was ice-cooled, and then 55% sodium hydride (0.340 g, 7.84 mmol) was added and stirred for 30 minutes. A solution of iodomethane (0.240 mL, 3.92 mmol) in DMF (3.5 mL) was added. The reaction mixture was allowed to warm to room temperature and stirred for 6 hours. 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 = 60:40 to 40:60) to obtain 2-chloro-4-methoxy-N-{4'-methoxy(1,1'-biphenyl)-4-yl}-N-methylbenzamide as a light brown oil (yield: 2.82 g, 91%). 1 H-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 solution of boron tribromide in dichloromethane (20 mL, 20.0 mmol) was added dropwise over 15 minutes. The reaction mixture was allowed to warm to room temperature, stirred for 16 hours, and then cooled to 0 °C again. Ice (100 g) was added, and the mixture was stirred at room temperature until the ice melted. The mixture was concentrated under reduced pressure, and the resulting solid was collected by filtration to give compound (3-11) as a white solid (yield: 1.65 g, 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). (Compound (3-11))

[0193] [ka]

[0194] <Synthesis Example 2> Deionized water (15 mL) was placed in a three-neck flask equipped with a dropping funnel, and compound (3-11) (0.531 g, 1.50 mmol) synthesized in Synthesis Example 1 and sodium hydroxide (0.120 g, 3.00 mmol) were added. After vigorously stirring to dissolve the substrate, a 2% aqueous solution of tetrabutylammonium bromide (0.6 mL) was added as a catalyst, and the atmosphere inside the apparatus was thoroughly purged with argon. A solution of terephthalic acid dichloride (0.305 g, 1.50 mmol) in chloroform (15 mL) was placed in the dropping funnel and quickly added dropwise to the system. After the addition was complete, the mixture was stirred vigorously at room temperature for 3 hours to allow interfacial polymerization. After the reaction, the solution was added dropwise to methanol (300 mL). The precipitate was filtered, washed with water (100 mL) and methanol (100 mL), and then vacuum dried to obtain polymer 1 (0.698 g, 96% yield). (Polymer 1)

[0195] [ka]

[0196] [Example 1] 3.6 wt% of polymer 1 and 0.4 wt% of dibutyl phthalate (molecular weight: 278) as a thermal reorientation promoter were dissolved in 96 wt% of 1,1,1,3,3,3-hexafluoro-2-propanol. This solution was cast onto a quartz glass substrate, spin-coated at 5000 rpm for 60 seconds, and dried in an oven at 60°C for 60 minutes to obtain a thin film (thickness 0.750 μm). The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0197] [Example 2] A thin film (film thickness: 0.724 μm) was obtained in the same manner as in Example 1, except that tributyl trimellitate (molecular weight: 378) was used as the thermal reorientation promoter. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0198] [Example 3] A thin film (film thickness: 0.757 μm) was obtained in the same manner as in Example 1, except that triethyl citrate (molecular weight: 276) was used as the thermal reorientation promoter. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0199] [Example 4] A thin film (thickness 0.868 μm) was obtained in the same manner as in Example 1, except that 3.8 wt% of polymer 1 and 0.2 wt% of tricresyl phosphate (molecular weight: 368) as a thermal reorientation promoter were dissolved in 96 wt% of 1,1,1,3,3,3-hexafluoro-2-propanol, and the solution was cast onto a quartz glass substrate and spin-coated at 3500 rpm for 60 seconds. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1. [Example 5] A thin film (film thickness 0.884 μm) was obtained in the same manner as in Example 1, except that tricresyl phosphate (molecular weight: 368) was used as a thermal reorientation promoter and spin-coated at 3500 rpm for 60 seconds. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0200] [Example 6] A thin film (thickness 1.028 μm) was obtained in the same manner as in Example 1, except that 3.4 wt% of polymer 1 and 0.6 wt% of tricresyl phosphate (molecular weight: 368) as a thermal reorientation promoter were dissolved in 96 wt% of 1,1,1,3,3,3-hexafluoro-2-propanol, and the solution was cast onto a quartz glass substrate and spin-coated at 3000 rpm for 60 seconds. The obtained thin film was irradiated with 7200 mJ / cm of polarized ultraviolet light at 313 nm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0201] [Example 7] A thin film (thickness 1.092 μm) was obtained in the same manner as in Example 1, except that 3.0 wt% of polymer 1 and 1.0 wt% of tricresyl phosphate (molecular weight: 368) as a thermal reorientation promoter were dissolved in 96 wt% of 1,1,1,3,3,3-hexafluoro-2-propanol, and the solution was cast onto a quartz glass substrate and spin-coated at 3000 rpm for 60 seconds. The obtained thin film was irradiated with 7200 mJ / cm of polarized ultraviolet light at 313 nm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0202] [Example 8] A thin film (thickness 1.297 μm) was obtained in the same manner as in Example 1, except that Adeka Cizer P-300 (molecular weight: 3000, adipic acid-based polyester) was used as a thermal reorientation promoter and spin-coated at 3000 rpm for 60 seconds. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0203] [Example 9] A thin film (thickness 1.287 μm) was obtained in the same manner as in Example 1, except that Irganox® 245 (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]) (molecular weight: 587) was used as a thermal reorientation promoter and spin-coated at 3000 rpm for 60 seconds. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0204] [Example 10] A thin film (thickness 1.118 μm) was obtained in the same manner as in Example 1, except that 3.6 wt% of polymer 1 and 0.4 wt% of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (molecular weight: 406) as a thermal reorientation promoter were dissolved in a 96 wt% solution of 1,1,1,3,3,3-hexafluoroisopropanol / chloroform = 4 / 1 (weight ratio) and spin-coated at 3000 rpm. 313 nm polarized ultraviolet light was irradiated on the obtained thin film at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0205] [Example 11] A thin film (thickness: 1.214 μm) was obtained in the same manner as in Example 1, except that isodecyl phosphite (molecular weight: 503) was used as a thermal reorientation promoter and spin-coated at 3000 rpm for 60 seconds. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0206] [Example 12] A thin film (film thickness 0.887 μm) was obtained in the same manner as in Example 1, except that didodecyl 3,3'-thiodipropionate (molecular weight: 515) was used as a thermal reorientation promoter and spin-coated at 3500 rpm for 60 seconds. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm.2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0207] [Example 13] A thin film (thickness: 0.986 μm) was obtained in the same manner as in Example 1, except that bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight: 509) was used as a thermal reorientation promoter and spin-coated at 3000 rpm for 60 seconds. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with a good appearance and high retardation. The retardation values ​​calculated for a film thickness of 10µm are shown in Table 1.

[0208] [Example 14] 1.8 wt% of polymer 1 and 0.2 wt% of tricresyl phosphate (molecular weight: 368) as a thermal reorientation promoter were dissolved in 98 wt% of 1,1,1,3,3,3-hexafluoro-2-propanol. This solution was cast onto a quartz glass substrate, spin-coated at 6000 rpm for 60 seconds, and dried in an oven at 60°C for 60 minutes to obtain a thin film (thickness 0.2 μm). The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190° C. to obtain a liquid crystal alignment film.

[0209] Using two 25 μm-thick PET films (Toray, product name: Lumirror(R) T60) cut into 1.5 mm x 20 mm pieces as spacers, two quartz glass plates with the liquid crystal alignment film laminated on them were stacked with the thin film facing inward and parallel to the direction of polarized UV light irradiation. The quartz glass plates were then glued together with instant adhesive (Toagosei, Aron Alpha 201) around the periphery, excluding the liquid crystal injection area, to form an empty liquid crystal cell. After bonding, 4-cyano-4'-pentylbiphenyl heated to 50°C was injected into the empty liquid crystal cell to form a liquid crystal cell. The resulting liquid crystal cell was observed under a polarizing microscope in three directions, with the polarizer angled at 0°, 45°, and 90° relative to the direction of polarized UV light irradiation of the thin film. The microscopic image changed from dark to light to dark, confirming the uniform alignment of the liquid crystal directors. Table 2 shows whether or not the liquid crystal alignment film could be produced by heating at 200°C or less.

[0210] [In this specification, the liquid crystal director refers to a vector of the direction in which the long axes of liquid crystal molecules are aligned (main alignment axis)] [Comparative Example 1] 4.0 wt% of polymer 1 was dissolved in 96 wt% of 1,1,1,3,3,3-hexafluoro-2-propanol. The solution was cast onto a quartz glass substrate, spin-coated at 5000 rpm for 60 seconds, and dried in an oven at 60°C for 60 minutes to obtain a thin film (thickness 0.837 μm). The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190° C. Although the appearance was good, a thin film showing a high retardation amount was not obtained. The retardation amount converted into a film thickness of 10 μm is shown in Table 1.

[0211] Comparative Example 2 3.6 wt% of polymer 1 and 0.4 wt% of dimethyl phthalate (molecular weight: 194) were dissolved in 96 wt% of 1,1,1,3,3,3-hexafluoro-2-propanol. This solution was cast onto a quartz glass substrate, spin-coated at 5000 rpm for 60 seconds, and dried in an oven at 60°C for 60 minutes to obtain a thin film (thickness 0.777 μm). The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2After irradiation, the film was heated at 190° C. Although the appearance was good, a thin film showing a high retardation amount was not obtained. The retardation amount converted into a film thickness of 10 μm is shown in Table 1.

[0212] Comparative Example 3 A thin film (film thickness: 0.890 μm) was obtained in the same manner as in Comparative Example 2, except that trimethyl phosphate (molecular weight: 140) was used as the additive. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190° C. Although the appearance was good, a thin film showing a high retardation amount was not obtained. The retardation amount converted into a film thickness of 10 μm is shown in Table 1.

[0213] Comparative Example 4 A thin film (thickness: μm) was obtained in the same manner as in Comparative Example 1, except that 2.6 wt% of Polymer 1 and 1.4 wt% of tricresyl phosphate (molecular weight: 368) as a thermal reorientation promoter were dissolved in 96 wt% of 1,1,1,3,3,3-hexafluoro-2-propanol, and the solution was cast onto a quartz glass substrate and spin-coated at 1500 rpm for 60 seconds. The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film with high retardation, but the appearance was poor, as the thermal reorientation promoter had oozed out. The retardation values ​​converted to a 10µm film thickness are shown in Table 1.

[0214] Comparative Example 5 2% by weight of polymer 1 was dissolved in 98% by weight of 1,1,1,3,3,3-hexafluoro-2-propanol. The solution was cast onto a quartz glass substrate, spin-coated at 7000 rpm for 60 seconds, and dried in an oven at 60°C for 60 minutes to obtain a thin film (thickness 0.2 μm). The obtained thin film was irradiated with 313 nm polarized ultraviolet light at 7200 mJ / cm. 2 After irradiation, the film was heated at 190°C to obtain a thin film.

[0215] Two 25 μm-thick PET films (Toray, product name: Lumirror(R) T60) cut into 1.5 mm x 20 mm pieces were used as spacers to stack two quartz glass plates with the thin film laminated on them, with the thin film facing inward and the direction of polarized UV light irradiation parallel. The quartz glass plates were then glued together with instant adhesive (Toagosei, Aron Alpha 201) around the periphery, excluding the liquid crystal injection area, to create an empty liquid crystal cell. After bonding, 4-cyano-4'-pentylbiphenyl heated to 50°C was injected into the empty liquid crystal cell to form a liquid crystal cell. The resulting liquid crystal cell was observed under a polarizing microscope in three directions, with the polarizer angled at 0°, 45°, and 90° relative to the direction of polarized UV light irradiation of the thin film. The microscopic image remained bright, confirming that the liquid crystal directors were not uniformly aligned. Table 2 shows whether or not a liquid crystal alignment film can be produced by heating at temperatures below 200°C.

[0216] Comparison with Comparative Example 4 makes it clear that the thin film of Example 11 can be used as a liquid crystal alignment film by irradiating it with polarized ultraviolet light and heating it at 200° C. or less.

[0217] [Table 1]

[0218] [Table 2]

[0219] The resin compositions of Examples 1 to 13, which contain 70 to 99.99% by weight of a polymer containing 1 to 50 mol% of a structural unit represented by formula (1) and 0.01 to 30% by weight of a thermal reorientation promoter having a molecular weight of 200 to 10,000, yield thin films with high retardation, whereas the resin compositions of Comparative Example 1, which does not use a thermal reorientation promoter, and Comparative Examples 2 and 3, which contain an additive with a molecular weight of less than 200, do not yield thin films with high retardation. Furthermore, when the thermal reorientation promoter is contained in an amount of 30% by weight or more, thin films with good appearance cannot be obtained.

Claims

1. A resin composition comprising 70 to 99.99% by weight of a polymer containing 1 to 50 mol% of a structural unit represented by the following formula (1), and 0.01 to 30% by weight of a plasticizer, an antioxidant, and a light stabilizer, each having a molecular weight of 200 to 10,000. 【Chemistry 1】 (In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a fused aromatic ring, the ring having an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-constituting atom, and these monocyclic aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have a substituent. R １ and R ２ may be the same or different and represent 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, and an optionally substituted aromatic group having 4 to 20 carbon atoms. X represents a group selected from the group consisting of an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. S １ and S ２ each independently represents an —O— group, a —(C═O)O— group, a —O(C═O)— group, or a —O(C═O)—O— group; and n is 0 or 1.

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

3. 3. The resin composition according to claim 1, comprising a polymer having a photoreactive structure and a structure derived from one or more compounds arbitrarily selected from the group consisting of dicarboxylic acids, dicarboxylic acid dichlorides, diamines, tetracarboxylic dianhydrides, polyhydric hydroxy compounds, and isocyanate compounds.

4. A resin composition obtained by subjecting the resin composition according to any one of claims 1 to 3 to a light irradiation treatment.

5. The method for producing the polymer according to any one of claims 1 to 3, comprising copolymerizing a monomer represented by the following general formula (2): 【Chemistry 2】 (In the formula, ring A, ring B, and ring C each independently represent a ring selected from the group consisting of a monocyclic aromatic ring, a polycyclic aromatic ring, and a fused aromatic ring, the ring having an atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-constituting atom, and these monocyclic aromatic rings, polycyclic aromatic rings, and fused aromatic rings may have a substituent. R １ and R ２ may be the same or different and represent 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, and an optionally substituted aromatic group having 4 to 20 carbon atoms. X represents a group selected from the group consisting of an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. Y represents a group selected from the group consisting of a hydrogen atom, an optionally substituted alkoxy group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted acyloxy group having 1 to 5 carbon atoms, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, an optionally substituted arylsulfonyloxy group having 6 to 11 carbon atoms, and an optionally substituted aryloxy group having 4 to 20 carbon atoms. F １ and F ２ each independently represents a group selected from the group consisting of a hydroxy group and a carboxy group; and n represents 0 or 1.

6. The monomer is represented by general formula (2), wherein ring A, ring B, and ring C are an optionally substituted monocyclic aromatic ring, an optionally substituted polycyclic aromatic ring, or an optionally substituted fused aromatic ring, each of which has an atom selected from the group consisting of carbon atoms and nitrogen atoms as ring-constituting atoms, and R １ and R ２ may be the same or different and are a group selected from the group consisting of a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms, the method for producing a polymer according to claim 5.

7. The method for producing a polymer according to claim 5 or 6, wherein the monomer represented by formula (2) is any one of the following formulas (2-1-1) to (2-1-9) and (2-2-1): 【Transformation 3】 (In the formula, R １ and R ２ are R in the formula (3), respectively. １ and R ２ is synonymous with. X ａ represents a group selected from the group consisting of a halogen atom, an optionally substituted alkylsulfonyloxy group having 1 to 5 carbon atoms, and 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 independently represents a hydroxy group or an amino group.

8. The method for producing a polymer according to any one of claims 5 to 7, wherein the monomer represented by formula (2) is any one of the following formulas (2-1-1-1) to (2-2-1-3): 【Chemistry 4】 (In the formula, R １ and R ２ are R in the formula (2), respectively. １ and R ２ is synonymous with

9. The method for producing the polymer according to any one of claims 5 to 8, wherein the monomer represented by formula (2) is copolymerized with at least one copolymerization monomer selected from the group consisting of dicarboxylic acids, dicarboxylic acid dichlorides, diamines, tetracarboxylic acid dianhydrides, polyvalent hydroxy compounds, and isocyanate compounds.

10. The resin composition according to any one of claims 1 to 4, wherein the thermal reorientation promoter is a plasticizer.

11. The resin composition according to any one of claims 1 to 4, wherein the thermal reorientation promoter is an antioxidant.

12. The resin composition according to any one of claims 1 to 4, wherein the thermal reorientation promoter is a light stabilizer.

13. An optical thin film comprising the resin composition according to any one of claims 1 to 4 and 10 to 13.

14. 14. The optical thin film according to claim 13, wherein the retardation (Re) measured using a 589 nm light source and converted to a film thickness of 10 μm and expressed by the following formula (A) is 100 nm or more after light irradiation treatment and heat baking treatment: Re=(ny-nx)×d (A) (In formula (A), nx represents the refractive index in the in-plane fast axis direction, ny represents the refractive index in the in-plane slow axis direction, and d represents the film thickness (nm).)

15. The optical thin film according to claim 14, wherein the light irradiation treatment is performed by irradiating with polarized ultraviolet light or obliquely incident ultraviolet light.

16. 16. The optical thin film according to claim 14, which exhibits a retardation of Re>100 nm or more when subjected to a heating and baking treatment at 200° C. or less after light irradiation.

17. A retardation film comprising the optical thin film according to any one of claims 14 to 16.

18. A liquid crystal alignment film comprising the optical thin film according to any one of claims 14 to 16.

Images