Polymer composition containing a photoreactive group, optical thin film

Abstract

To provide a composition of a polymer which exhibits a high phase difference even under a low heating temperature.SOLUTION: A resin composition is provided, containing: 80-99.99 wt.% of unsaturated polyester composed of a bisphenol residue having two cinnamoyl groups between two phenols, a bisphenol residue having two tertiary amino groups between two phenols, and a phthalic acid residue; and 0.01-20 wt.% of a thermal reorientation accelerator having a molecular weight of 200 or more and 10,000 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polymer composition containing a photoreactive group. More specifically, it relates to a polymer composition containing a photoreactive group and a retardation film containing the composition.

Background Art

[0002] Retardation films are used in various image display devices from the viewpoint of viewing angle expansion and the like. As existing retardation films, those made using polymerizable liquid crystalline compounds are known. At this time, in order to orient the polymerizable liquid crystalline compound, it is necessary to provide an alignment film on a support that forms an optically anisotropic layer, and an alignment film subjected to rubbing treatment or photo-alignment treatment is used (see, for example, Patent Documents 1 to 3). However, both require complex manufacturing equipment and processes, and there are also problems in terms of product yield. In addition, a proposal has been made to form an optical thin film and a retardation film having a retardation Re / thickness of 100 nm or more by using a side-chain type liquid crystal acrylate resin containing a photoreactive group without using an alignment film, by means of polarized ultraviolet irradiation and heat treatment (see, for example, Patent Documents 4 and 5). However, side-chain type liquid crystal acrylate resins containing photoreactive groups have problems such as requiring multiple steps in the synthesis of monomers, being expensive, and having a low heat resistance temperature. Linear liquid crystal polyester resins containing photoreactive groups do not require an alignment film and can form optical thin films and retardation films by polarized ultraviolet irradiation and heat treatment, and it is expected to produce optical thin films and retardation films with excellent heat resistance from inexpensive monomers. However, linear liquid crystal polyester resins have the problem of requiring a high processing temperature of 200 degrees or more while having excellent heat resistance (see, for example, Patent Documents 6 to 8). Therefore, when applying a linear liquid crystal polyester resin as an optical thin film and a retardation film, for example, there is a problem that inexpensive general-purpose resin film support substrates such as polyethylene terephthalate (heat resistance temperature of about 160 ° C), polyethylene naphthalate (heat resistance temperature of about 200 ° C), and cycloolefin polymer (heat resistance temperature of about 160 ° C) cannot be used.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention has been made in view of the above problems, and an object thereof is to provide a polymer composition that is oriented even at a low heating temperature of 200°C or lower and exhibits a high retardation of 100 nm or more in terms of retardation Re / thickness.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a polymer having a specific photoreactive group and a specific additive solves the above problems, promotes the thermal reorientability of the polymer at a heat treatment temperature equal to or lower than the heat resistance temperature of a general-purpose resin film support substrate, and can be manufactured on a general-purpose resin film support substrate, thus completing the present invention.

[0006] That is, one aspect of the present invention relates to a resin composition containing 80 to 99.99% by weight of a polymer having a structural unit A represented by the following formula (1) and at least one of a structural unit B represented by the following formula (2) or a structural unit C represented by the following formula (3), and 0.01 to 20% by weight of a thermal reorientation accelerator having a molecular weight of 200 or more and 10,000 or less.

[0007] [Chemical formula]

[0008] (In formula (1), X 1 ~X 3 each independently represents either an aromatic ring having 5 to 7 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring or the alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Here, the substituents in X 1 ~X 3 each independently represent one kind of the group consisting of a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and when X 1 ~X 3 do not have a substituent, they are hydrogen atoms. Y 1 and Y 2 each independently represent one kind of the group consisting of -O-, -CO-, -NR 9 -. Here, R 9 represents one kind of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Ar 1 and Ar 2 each independently represent an aromatic ring having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Here, the substituents in Ar 1 and Ar 2 each independently represent one kind of the group consisting of a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and when Ar 1 and Ar 2 do not have a substituent, they are hydrogen atoms. R 1 ~R4 each independently represents one member selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. L 1 and L 4 represents one member selected from the group consisting of a single bond, -O-, -NR 5 -. Here, R 5 represents one member selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. L 2 and L 3 represents one member selected from the group consisting of a single bond, -O-, -CO-O-, -CO-NR 6 -, -CO-, -CR 7 R 8 -. Here, R 6 represents one member selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. R 7 and R 8 each independently represents one member selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 5 carbon atoms. a and b each independently represent 0 or 1.)

[0009]

Chemical formula

[0010] (In formula (2), Y 3 and Y 4 each independently represents one member selected from the group consisting of -O-, -CO-, -NR 10 -. Here, R 10 represents one member selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. X 4 to X 6 each independently represents either an aromatic ring having 5 to 7 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring or the alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. R 11 and R 12 represent one member selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. c represents 0 or 1.)

[0011] [Chemical formula]

[0012] (In formula (3), Y 5 and Y 6 each independently represents one member selected from the group consisting of -O-, -CO-, -NR 13 -. Here, R 13 represents one member selected from the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z represents one member selected from the group consisting of an alicyclic hydrocarbon group having 5 to 7 carbon atoms, a linear alkylene group having 2 to 20 carbon atoms, and a branched alkylene group having 4 to 20 carbon atoms.)

[0013] Another aspect of the present invention relates to an optical thin film containing the above composition.

[0014] Another aspect of the present invention relates to a retardation film provided with the above thin film.

[0015] Furthermore, another aspect of the present invention relates to a liquid crystal alignment film provided with the above thin film. [Advantages of the Invention]

[0016] According to the present invention, since a high retardation is exhibited even at a heat treatment temperature of 200°C or lower, it is possible to provide a composition, an optical thin film, and a retardation film made therefrom that exhibit reactivity to ultraviolet light and can be formed on a general-purpose resin substrate. [Modes for Carrying Out the Invention]

[0017] The composition, which is one aspect of the present invention, will be described in detail below.

[0018] As one aspect of the present invention, there can be mentioned a composition (hereinafter referred to as "the composition of the present invention") containing 80 to 99.99% by weight of a polymer having a structural unit A represented by the following formula (1) and at least one of a structural unit B represented by the following formula (2) or a structural unit C represented by the following formula (3), and 0.01 to 20% by weight of a thermal reorientation accelerator having a molecular weight of 200 or more and 10,000 or less.

[0019]

Chemical formula

[0020] (In formula (1), X 1 ~X 3 each independently represents either an aromatic ring having 5 to 7 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring or the alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Here, the substituents in X 1 ~X 3 each independently represent one kind of the group consisting of a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and when X 1 ~X 3 has no substituent, it is a hydrogen atom. Y 1 and Y 2 each independently represent one kind of the group consisting of -O-, -CO-, -NR 9 -. Here, R 9 represents one kind of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Ar 1 and Ar 2 each independently represent an aromatic ring having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Here, the substituents in Ar 1 and Ar 2 each independently represent one kind of the group consisting of a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, and when Ar 1 and Ar 2 has no substituent, it is a hydrogen atom. R1 ~R 4 each independently represents one member of the group consisting of a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. L 1 and L 4 represent one member of the group consisting of a single bond or -O-, -NR 5 -. Here, R 5 represents one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. L 2 and L 3 represent one member of the group consisting of a single bond or -O-, -CO-O-, -CO-NR 6 -, -CO-, -CR 7 R 8 -. Here, R 6 represents one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 7 and R 8 each independently represents one member of the group consisting of a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. a and b each independently represent 0 or 1.)

[0021]

Chemical formula

[0022] (In formula (2), Y 3 and Y 4 each independently represents one member of the group consisting of -O-, -CO-, -NR 10 -. Here, R 10 represents one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X 4 ~X 6 each independently represents either an aromatic ring having 5 to 7 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring or the alicyclic hydrocarbon group may be substituted by a nitrogen atom, an oxygen atom, or a sulfur atom. R 11 and R 12 represent one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. c represents 0 or 1.)

[0023]

Chem.

[0024] (In formula (3), Y 5 and Y 6 each independently represents one member of the group consisting of -O-, -CO-, -NR 13 -. Here, R 13 represents one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z represents one member of the group consisting of an alicyclic hydrocarbon group having 5 to 7 carbon atoms, a linear alkylene group having 2 to 20 carbon atoms, and a branched alkylene group having 4 to 20 carbon atoms.)

[0025] In formula (1), X 1 ~X 3 each independently represents either an aromatic ring having 5 to 7 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring or the alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Here, as the substituents in X 1 ~X 3 , a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms can be mentioned. When X 1 ~X 3 has no substituent, it is a hydrogen atom. X 1 ~X 3 is preferably one member of the group consisting of a benzene ring, a methylbenzene ring, a t-butylbenzene ring, a dimethylbenzene ring, a tetrafluorobenzene ring, or a cyclohexane ring, and more preferably a trans-cyclohexane ring.)

[0026] Y 1 and Y 2 each independently represents one member of the group consisting of -O-, -CO-, -NR 9 -. Here, R 9 represents one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Y 1 and Y 2 are preferably -O-.)

[0027] Ar 1 and Ar 2 each independently represents an aromatic ring having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom. Here, Ar 1 and Ar 2 Examples of the substituent in Ar 1 and Ar 2 include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. When Ar 1 and Ar 2 do not have a substituent, it is a hydrogen atom. Ar

[0028] R 1 ~R 4 each independently represents one member selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. R 1 ~R 4 is preferably a hydrogen atom or a cyano group, and more preferably a hydrogen atom.

[0029] L 1 and L 4 each independently represents one member selected from the group consisting of a single bond, -O-, and -NR 5 -. L 1 and L 4 are preferably -O- or -NR 5 -. The R 1 in L 4 represents one member selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms in R 5 include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. 5

[0030] L 2 and L 3 ​is, independently of each other, a single bond or -O-, -CO-O-, -CO-NR 6 -, -CO-, -CR 7 R 8 -, representing one kind of the group consisting of them. However, L 2 and L 3 may have the reverse left - right relationship. L 2 and L 3 are preferably a single bond or -CO-NR 6 -, and more preferably a single bond. R 2 and L 3 in R 6 represents one kind of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms in R 6 include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. L 2 and L 3 in R 7 and R 8 each independently represent one kind of the group consisting of a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. Examples of the halogen atom in R 7 and R 8 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 5 carbon atoms in R 7 and R 8 include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

[0031] a and b each independently represent 0 or 1.

[0032] In formula (2), Y 3 and Y 4 each independently represent one kind of the group consisting of -O-, -CO-, -NR 10 -. Here, R 10 represents one kind of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Y 3 and Y 4 are preferably -O- or -CO-.

[0033] X4 ~X 6 each independently represents either an aromatic ring having 5 to 7 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring or the alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Here, X 4 ~X 6 Examples of the substituent in ~X 4 ~X 6 include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. When X 4 ~X 6 has no substituent, it is a hydrogen atom. X

[0034] R 11 and R 12 each represent one kind selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms in R 5 include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

[0035] c represents 0 or 1.

[0036] In formula (3), Y 5 and Y 6 each independently represent one kind selected from the group consisting of -O-, -CO-, -NR 13 -. Here, R 13 represents one kind selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. Y 5 and Y 6 are preferably -CO-.

[0037] Z represents one kind of the group consisting of an alicyclic hydrocarbon group having 5 to 7 carbon atoms, a linear alkylene group having 2 to 20 carbon atoms, and a branched alkylene group having 4 to 20 carbon atoms. Z is preferably an alicyclic hydrocarbon group having 5 to 7 carbon atoms or a linear alkylene group having 2 to 20 carbon atoms, and more preferably an alicyclic hydrocarbon group having 5 to 7 carbon atoms or a linear alkylene group having 2 to 10 carbon atoms.

[0038] The copolymer contained in the composition of the present invention preferably contains a structural unit A containing a cinnamoyl group represented by the following formula (4) 1 and a structural unit C represented by the following formula (5) 1 and is a polymer having the same.

[0039]

Chemical formula

[0040] (In formula (4), X 7 and X 8 each independently represents either an aromatic ring having 5 to 7 carbon atoms which may have a substituent or an alicyclic hydrocarbon group having 5 to 7 carbon atoms which may have a substituent. L 5 represents a single bond or one kind of the group consisting of -O-, -CO-O-, -CO-NR 16 -, -CO-, -CR 17 R 18 -. Here, R 16 represents either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 17 and R 18 each independently represents one kind of the group consisting of a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. m and l each independently represent 0 or 1. R 14 and R 15 each independently represents one kind of the group consisting of a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. n 1 and n 2 each independently represents an integer from 0 to 4.)

[0041] [Chemical formula]

[0042] (In formula (5), Z represents either a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 4 to 20 carbon atoms.)

[0043] In the copolymer contained in the composition of the present invention, the structural unit A 1 is preferably the structural unit A represented by the following formula (6). 2

[0044] [Chemical formula]

[0045] (In formula (6), Y 7 represents one kind of the group consisting of a benzene ring, a biphenyl ring, a cyclohexane ring, and a bicyclohexane ring, which may have a substituent. R 14 and R 15 each independently represent a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. n 1 and n 2 each independently represent an integer of 0 to 4.)

[0046] The method for synthesizing the copolymer contained in the composition of the present invention is not particularly limited and can be synthesized by a polymerization method known in the art, for example, a melt polymerization method or a solution polymerization method using the corresponding dicarboxylic acid chloride. Among these, the solution polymerization method capable of polymerization under mild conditions is particularly preferred. Specifically, in a solvent, the compound of the present invention may be subjected to interfacial polycondensation with at least one of the compound having the structural unit B or the compound having the structural unit C.

[0047] Since the polymerization reaction does not proceed in the polymer not containing the structural unit A represented by formula (1), even when subjected to polarized ultraviolet irradiation, oblique incident ultraviolet irradiation, and heat treatment, the thin film made of the polymer does not exhibit excellent liquid crystal alignment properties.

[0048] A polymer that does not contain the structural unit B represented by the formula (2) and the structural unit C represented by the formula (3) has low thermal orientation properties. Therefore, even when subjected to polarized ultraviolet irradiation, oblique incident ultraviolet irradiation, and heat treatment, a thin film made of the polymer does not exhibit excellent liquid crystal orientation properties.

[0049] The composition of the present invention contains a thermal reorientation accelerator. The optical thin film and the retardation film obtained by using the composition of the present invention have improved molecular mobility due to the thermal reorientation accelerator. Therefore, the thermal reorientation treatment of the polymer can be performed even on a general-purpose resin support substrate having a low heat resistance temperature.

[0050] The thermal reorientation accelerator contained in the composition of the present invention has a molecular weight of 200 or more and 10,000 or less. When the molecular weight is less than 200, problems such as precipitation and exudation of the additive at high temperature or volatilization of the additive at high temperature occur, and the performance as an optical thin film cannot be maintained. When the molecular weight is greater than 10,000, the efficiency of improving the molecular orientation of the polyester is poor. The thermal reorientation accelerator of the present invention preferably has a molecular weight of 300 or more and 10,000 or less because of its low volatility during heat treatment.

[0051] The blending ratio of the polymer and the thermal reorientation accelerator in the composition of the present invention is 80 to 99.99% by weight of the polymer and 0.01 to 20% by weight of the thermal reorientation accelerator. More preferably, it is 85 to 99.9% by weight of the polymer and 0.1 to 15% by weight of the thermal reorientation accelerator due to the problem of precipitation and exudation of the thermal reorientation accelerator at high temperature. Particularly preferably, it is 85 to 99.0% by weight of the polymer and 1.0 to 15% by weight of the thermal reorientation accelerator from the viewpoint of thermal reorientation promotion efficiency. In the present invention, when the ratio of the thermal reorientation accelerator is less than 0.01% by weight, it becomes difficult to promote thermal reorientation, and when it is greater than 20% by weight, precipitation and exudation of the thermal reorientation accelerator are likely to occur.

[0052] Examples of the thermal reorientation accelerator of the present invention include plasticizers, antioxidants, and light stabilizers.

[0053] Examples of the plasticizer include carboxylic acid esters, phosphate esters, and polymer-based plasticizers.

[0054] Specific examples of the carboxylic acid ester include phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, citric acid ester, oleic acid ester, ricinoleic acid ester, sebacic acid ester, stearic acid ester, adipic acid ester, epoxidized ester, and the like.

[0055] Specific examples of the polymer plasticizer include polyester plasticizer, polyether plasticizer, and the like.

[0056] The heat reorientation accelerator of the present invention is preferably a plasticizer.

[0057] The phthalic acid ester cited as the heat reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (7).

[0058]

Chemical formula

[0059] (In formula (7), R 19 and R 20 each independently represent one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. Due to the low volatility during heat treatment, R 19 and R 20 are each independently preferably having 2 or more carbon atoms.)

[0060] The trimellitic acid ester cited as the heat reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (8).

[0061]

Chemical formula

[0062] (In formula (8), R 21 ~R 23 each independently represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0063] The pyromellitic acid ester cited as the thermal reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (9).

[0064]

Chemical formula

[0065] (In formula (9), R 24 ~R 27 each independently represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0066] The citric acid ester cited as the thermal reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (10).

[0067]

Chemical formula

[0068] (In formula (10), R 28 ~R 30 each independently represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. R 31represents one selected from the group consisting of a hydrogen atom, an acetyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0069] The oleic acid ester cited as the thermal reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (11).

[0070] [Chemical formula]

[0071] (In formula (11), R 32 represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0072] The ricinoleic acid ester cited as the thermal reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (12).

[0073] [Chemical formula]

[0074] (In formula (12), R 33 represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. R 34 represents one selected from the group consisting of a hydrogen atom, an acetyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0075] The sebacic acid ester cited as the heat reorientation promoter of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (13).

[0076]

Chemical formula

[0077] (In formula (13), R 35 and R 36 each independently represent one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0078] The stearic acid ester cited as the heat reorientation promoter of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (14).

[0079]

Chemical formula

[0080] (In formula (14), R 37 represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0081] The adipic acid ester cited as the heat reorientation promoter of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (15).

[0082]

Chemical formula

[0083] (In formula (15), R 38 and R 39Each independently represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. Due to low volatility during heat treatment, R 38 and R 39 are each independently preferably having 2 or more carbon atoms. )

[0084] The epoxidized ester cited as the heat reorientation accelerator of the present invention has a molecular weight of 200 or more and is not particularly limited as long as it has one or more epoxy groups and ester bonds. For example, 4,5-epoxycyclohexane-1,2-dicarboxylic acid di-2-ethylhexyl, 4,5-epoxycyclohexane-1,2-dicarboxylic acid di(9,10-epoxystearyl), epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid isobutyl, epoxidized fatty acid 2-ethylhexyl, etc. can be cited.

[0085] Examples of the phosphate ester include compounds represented by the following formula (16).

[0086] [Chemical formula]

[0087] (In formula (16), R 40 ~R 42 each independently represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. Due to low volatility during heat treatment, R 40 ~R 42 are each independently preferably having 3 or more carbon atoms. )

[0088] The polyester plasticizer cited as the heat reorientation accelerator of the present invention is a polymer containing a structural unit represented by the following formula (17), and refers to those having a molecular weight of 200 or more and 10,000 or less.

[0089] [Chemical formula]

[0090] (In formula (17), R 43 and R 44 each independently represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0091] The polyether plasticizer cited as the thermal reorientation accelerator of the present invention is a polymer containing a structural unit represented by the following formula (18), and refers to those having a molecular weight of 200 or more and 10,000 or less.

[0092] [Chemical formula]

[0093] (In formula (18), R 45 represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0094] Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants, hydroxylamine antioxidants, vitamin E antioxidants, and other antioxidants.

[0095] The thermal reorientation accelerator of the present invention is preferably an antioxidant.

[0096] The phenolic antioxidant cited as the thermal reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less and containing the structure represented by the following formula (19).

[0097] [Chemical formula]

[0098] (In Formula (19), R 50 , R 51 Among them, at least one represents one selected from the group consisting of a secondary alkyl group having 2 to 20 carbon atoms, a tertiary alkyl group having 2 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 condensed aromatic ring. These may have either a substituent or an unsaturated bond. The other represents a hydrogen atom, an 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 condensed aromatic ring. These may have either a substituent or an unsaturated bond. Although these structures are not particularly limited, from the viewpoint of availability, a tert-butyl group is particularly preferred. R 48 ~R 50 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring. These may have either a substituent or an unsaturated bond.)

[0099] The phenolic antioxidants that can be mentioned as the thermal reorientation accelerator of the present invention are not limited to those represented by Formula (19). For example, galvinoxyl free radical, 3,3’,5,5’-tetra-tert-butyl-4,4’-stilbenequinone, 4-(hexyloxy)-2,3,6-trimethylphenol, etc. can also be mentioned.)

[0100] The amine antioxidants that can be mentioned as the thermal reorientation accelerator of the present invention refer to those having a structure represented by the following Formula (20) and having a molecular weight of 200 or more and 10,000 or less.)

[0101] [Chemical formula]

[0102] (In formula (20), Ar 3 represents a ring selected from the group consisting of an aromatic ring, a polycyclic aromatic ring, or a condensed aromatic ring having, as ring-constituting atoms, atoms 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 condensed aromatic rings may have a substituent. R 51 represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. Due to low volatility during heat treatment, R 51 is preferably 9 or more carbon atoms.)

[0103] The amine-based antioxidant that can be cited as the heat reorientation accelerator of the present invention is not limited to those represented by formula (20), and examples thereof include 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, poly(2,2,4-trimethyl-1,2-dihydroquinoline), and the like.

[0104] The phosphorus-based antioxidant that can be cited as the heat reorientation accelerator of the present invention refers to those having a structure represented by the following formula (21) and having a molecular weight of 200 or more and 10,000 or less.

[0105] [Chemical formula]

[0106] (In formula (21), R 52 and R 53 each independently represent one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. R 54 represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. Due to low volatility during heat treatment, R 52 , R 53and R 54 is preferably 3 or more carbon atoms independently. )

[0107] The sulfur-based antioxidant cited as the heat reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less, including the structure represented by the following formula (22).

[0108] [Chemical formula]

[0109] (In formula (22), R 55 represents one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, a heterocyclic ring, an aromatic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. R 56 represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. Due to low volatility during heat treatment, R 55 and R 56 are preferably 6 or more carbon atoms independently. )

[0110] Examples of the light stabilizer include hindered amine light stabilizers.

[0111] The heat reorientation accelerator of the present invention is preferably a light stabilizer.

[0112] The hindered amine light stabilizer cited as the heat reorientation accelerator of the present invention refers to those having a molecular weight of 200 or more and 10,000 or less, having the structural unit represented by the following formula (23).

[0113] [Chemical formula]

[0114] (In formula (23), Y 8represents one kind selected from the group consisting of -O-, -CO-, -NR 57 -. Here, R 57 represents one kind selected from the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 58 ~R 61 each independently represents one kind selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, a heterocyclic ring, an aromatic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond. Among these, a methyl group is particularly preferable from the viewpoint of availability. R 62 represents one kind selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alicyclic hydrocarbon atom, an aromatic ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, and these may have either a substituent or an unsaturated bond.)

[0115] Among these various additives, a plasticizer is preferable because it is easily available, has good compatibility with the resin, and is particularly excellent in promoting thermal reorientation even after being added to the resin. These thermal reorientation promoters may be used alone or in combination of two or more.

[0116] The thermal reorientation promoter of the present invention may be added for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor transmission rate, improving thermal stability, improving weather resistance, etc., in addition to the purpose of improving thermal reorientation property.

[0117] The resin composition of the present invention may contain other polymers, surfactants, polyelectrolytes, conductive complexes, pigments, dyes, antistatic agents, antiblocking agents, lubricants, etc., within a range not exceeding the gist of the invention.

[0118] The resin composition of the present invention can be obtained by blending a polyester resin having a photoreactive group and a thermal reorientation promoter (hereinafter referred to as resin, etc.).

[0119] As blending methods, methods such as melt blending and solution blending can be used. The melt blending method is a method of manufacturing by melting and kneading resins or the like by heating. The solution blending method is a method of dissolving resins or the like in a solvent and blending them. As solvents used for solution blending, for example, halogen-based solvents such as 1,1,1,3,3,3-hexafluoroisopropanol, methylene chloride, and chloroform; aromatic solvents such as toluene and xylene; ketone-based solvents such as cyclopentanone, acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, and propanol; ether solvents such as dioxane and tetrahydrofuran; dimethylformamide, N-methylpyrrolidone, etc. can be used. It is also possible to blend after dissolving resins or the like in a solvent, and it is also possible to dissolve powders, pellets, etc. of each resin in a solvent after kneading. It is also possible to pour the obtained blend resin solution into a poor solvent to precipitate the resin composition, and it is also possible to use the blend resin solution as it is for the production of an optical film.

[0120] Within the scope not exceeding the gist of the invention, the composition of the present invention may be blended with other polymers, crystal nucleating agents, surfactants, polyelectrolytes, conductive complexes, inorganic fillers, pigments, antistatic agents, antiblocking agents, lubricants, etc.

[0121] The composition of the present invention can be used in the form of a thin film. Thereby, optical properties are exhibited, and it can be used as an optical thin film (hereinafter referred to as "the thin film of the present invention"). There is no particular limitation on the method for manufacturing the thin film, and examples thereof include methods such as a melt film-forming method and a solution casting method.

[0122] (Melt film-forming method) Specifically, the method of melt film-forming includes a melt extrusion method using a T-die, a calendar molding method, a hot press method, a coextrusion method, a co-melting method, a multi-layer extrusion, an inflation molding method, etc., and is not particularly limited.

[0123] (Solution casting method) The solution casting method is a method of obtaining a thin film by casting a solution in which a composition is dissolved in a solvent (hereinafter referred to as "dope for casting") on a support substrate and then removing the solvent by heating or the like. At that time, as a method of casting the dope for casting on the support substrate, a spin coating method, a T-die method, a doctor blade method, a bar coater method, a roll coater method, a lip coater method, etc. are used. In particular, industrially, the method of continuously extruding the dope for casting from a die onto a belt-shaped or drum-shaped support substrate is the most common. Examples of the support substrate used include a glass substrate, a metal substrate such as stainless steel and ferrotpe, and films such as polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, and polyimide.

[0124] From the viewpoint of compatibility with thinning of optical members, the optical thin film using the thin film of the present invention preferably has a thickness of 0.01 to 20 μm, and particularly preferably 1 to 20 μm from the viewpoint of film thickness yield.

[0125] (Surfactant) The thin film of the present invention may contain at least one kind of surfactant in order to reduce film thickness unevenness. Examples of the surfactant that can be contained include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkyl ethylene oxide derivatives, polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, etc., and particularly fluorine-containing surfactants are preferred.

[0126] As described above, the thin film of the present invention can be suitably used as an optical thin film, and particularly since it exhibits a phase difference, it can be suitably used as a phase difference film.

[0127] The thin film of the present invention exhibits a phase difference when irradiated with ultraviolet light. The ultraviolet light may be polarized ultraviolet light or obliquely incident ultraviolet light. At this time, the wavelength of the ultraviolet light is preferably 200 nm or more and 400 nm or less, and particularly preferably 248 nm or more and 365 nm or less from the viewpoint of lamp handling. The irradiation energy amount is preferably 10 mJ / cm 2 or more and 10000 mJ / cm 2 or less, and from the viewpoint of productivity, it is particularly preferably 10 mJ / cm 2 or more and 5000 mJ / cm 2 or less.

[0128] After performing the ultraviolet irradiation, the thin film of the present invention is further heat-treated. Thereby, a phase difference is exhibited. From the viewpoint of the heat resistance of the resin film support substrate, the heat treatment temperature is preferably 50°C or more and 200°C or less.

[0129] The thin film of the present invention can be used as a retardation film by performing polarized ultraviolet irradiation or obliquely incident ultraviolet irradiation and further performing heat treatment to exhibit three-dimensional refractive index anisotropy.

[0130] The retardation characteristics of the optical thin film using the thin film of the present invention vary depending on the target retardation film. For example, the in-plane retardation (Re) in terms of 10 μm shown by the following formula (A) is preferably 80 nm or more, more preferably 100 to 10000 nm, and particularly preferably 100 to 5000 nm. The retardation characteristics at this time are measured under the condition of a measurement wavelength of 589 nm using a sample tilt type automatic birefringence meter (manufactured by AXOMETRICS, trade name: AxoScan). Re = (ny - nx) × d (A) (In the formula, 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 thickness.)

[0131] Since the thin film of the present invention exhibits a phase difference, it can be used as a retardation film. When used as a retardation film, it may be used as a single film or as a multilayer film in which other films are laminated. As the film laminated on the thin film of the present invention, the thin film of the present invention may be used, or a resin film such as a polymerizable liquid crystal film, a sputtered film, polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, or polyimide may be used.

[0132] Since the thin film of the present invention aligns the liquid crystal compound on the film, it can be used as a liquid crystal alignment film.

Examples

[0133] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not construed as being limited thereto.

[0134] <Measurement of Nuclear Magnetic Resonance Spectrum> Using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., trade name: ECZ 400S), 1 the 1H-NMR spectrum was measured.

[0135] <Polarized Ultraviolet Irradiation> Ultraviolet light was irradiated using a mercury light source (manufactured by Asahi Spectra Co., Ltd., trade name: REX-250) incorporated with a band-pass filter (248 nm). When irradiating polarized ultraviolet light, only P-polarized light was irradiated with a polarization beam splitter of the corresponding wavelength.

[0136] <Heat Treatment> Heat treatment was performed using either an inert oven (manufactured by ESPEC, trade name: IPHH-202) in a non-oxidizing atmosphere.

[0137] <Measurement of Retardation Characteristics> Using a sample tilt type automatic birefringence meter (manufactured by AXOMETRICS, trade name: AxoScan), the retardation characteristics of the retardation film were measured using light with a wavelength of 589 nm.

[0138] <Measurement of Film Thickness of Thin Film> The film thickness of the thin film was measured using a spectroscopic ellipsometer (manufactured by J.A. Woollam, product name: RC2-U).

[0139] <Polarizing microscope observation> Using a microscope (manufactured by Olympus, product name: BX53), a polarizing condenser (manufactured by Olympus, product name: U-POC-2), and an analyzer (manufactured by Olympus, product name: U-AN360P-2), the low-molecular liquid crystal on the thin film was observed, and the liquid crystal alignment was observed.

[0140] <Synthesis Example 1> Using the method described in Chinese Journal of chemistry, 23, 1523, 2005., tetrahydropyranyl-coumaric acid (10 g, 40.3 mmol) with the phenol site protected, trans-cyclohexanediol (2.29 g, 19.7 mmol), and 4-dimethylaminopyridine (2.5 g) as a base catalyst were dissolved in dehydrated dichloromethane (100 ml) at 0 °C under a nitrogen stream. 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide (8.49 g, 44.3 mmol) was added thereto, and the mixture was returned to room temperature and reacted overnight. Water was added to stop the reaction, and the solvent was distilled off under reduced pressure. The residue was redissolved in tetrahydrofuran (200 ml), 2N hydrogen chloride (40 ml) was added, and the mixture was stirred at room temperature for two hours. The precipitate was filtered to obtain 6.74 g of Compound 1. 1 The results of the H-NMR spectrum are shown below. 1 H-NMR(400MHz,(CD 3 ) 2 SO):δ7.53-7.49(m,6H),6.76-6.73(m,4H),6.38-6.31(m,2H),4.79(brs,2H),1.94(brs,4H),1.54(brs,4H). (Compound 1)

[0141]

Chemical formula

[0142] <Synthesis Example 2> Under a nitrogen stream, a mixture of 4-methoxy-N-methylaniline (3.00 g, 21.9 mmol), tetrahydrofuran (20 mL), and water (20 mL) was cooled with ice, and then sodium hydrogen carbonate (11 g) was added. While stirring the mixture, a solution of terephthaloyl chloride (2.17 g, 10.7 mmol) in tetrahydrofuran (20 mL) was slowly added, and the mixture was stirred under ice-cooling for 3 hours. Water (500 mL) was added to the reaction mixture, and the resulting solid was collected by filtration and washed with 2N hydrochloric acid (200 mL) and methanol (300 mL) to obtain N,N'-bis(4-methoxyphenyl)-N,N'-dimethyl-1,4-benzenedicarboxamide (3.91 g, yield: 90%). 1 The results of the 1H-NMR spectrum are shown below. 1 1H-NMR(400MHz,(CD 3 ) 2 SO):δ7.07(s,4H),6.83(d,J = 8.0Hz,4H),6.67(d,J = 8.0Hz,4H),3.73(s,6H),3.38(s,6H). The N,N'-bis(4-methoxyphenyl)-N,N'-dimethyl-1,4-benzenedicarboxamide (1.00 g, 2.47 mmol) obtained above was dissolved in dichloromethane (25 mL), and then a 1 mol / L boron tribromide dichloromethane solution (7.4 mL) was added dropwise over 5 minutes under ice-cooling. After the reaction system was warmed to room temperature, it was stirred for 15 hours, and the reaction mixture was added to ice-cooled water (300 mL). The solid formed in the system was collected by filtration and washed with water (500 mL) to obtain a brown solid (776 mg, 83%) of Compound 2. 1 The results of the 1H-NMR spectrum are shown below. 1 1H-NMR(400MHz,(CD 3 ) 2 SO):δ9.55 - 9.28(br,2H),6.98(s,4H),6.87 - 6.67(m,4H),6.58 - 6.49(m,4H),3.20(s,6H). (Compound 2)

[0143]

Chemical Structure

[0144] <Synthesis Example 3> 18.5 mL of ion-exchanged water was placed in a three-necked flask equipped with a dropping funnel, and Compound 1 (0.160 g, 0.392 mmol), Compound 2 (1.24 g, 3.29 mmol), and sodium hydroxide (0.300 g, 7.50 mmol) were dissolved and stirred. A 2.0 wt% aqueous solution of tetra-n-butylammonium bromide (1.5 mL) as a catalyst was added, and the inside of the apparatus was purged with nitrogen. A solution prepared by dissolving Compound 3 (0.773 g, 3.70 mmol) in chloroform (18.5 mL) was placed in the dropping funnel, added dropwise, and then stirred at room temperature for 3 hours. The reaction solution was poured into methanol, and the precipitate was filtered off and then dried under vacuum to obtain Polymer 1 (yield 88%). (Compound 3)

[0145] [Chemical formula]

[0146] [Example 1] 4.5 wt% of Polymer 1 and 0.5 wt% of dibutyl phthalate (molecular weight: 278) as a heat reorientation accelerator were dissolved in 95 wt% of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 6000 rpm for 60 seconds, and then dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness 0.847 μm). When the obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heated at 150 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0147] [Example 2] 5.0 wt% of Polymer 1 and 0.56 wt% of ditridecyl phthalate (molecular weight: 531) as a thermal reorientation promoter were dissolved in 94.44 wt% of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 6000 rpm for 60 seconds, and then dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness 0.941 μm). After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After heating at 140 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0148] [Example 3] A thin film (film thickness 0.916 μm) was obtained in the same manner as in Example 2 except that bis(2-ethylhexyl) isophthalate (molecular weight: 391) was used as the thermal reorientation promoter. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After heating at 140 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0149] [Example 4] A thin film (film thickness 0.714 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. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After heating at 150 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0150] [Example 5] A thin film (film thickness 0.955 μm) was obtained in the same manner as in Example 2 except that tris(2-ethylhexyl) trimellitate (molecular weight: 547) was used as the thermal reorientation promoter. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After heating at 140 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0151] [Example 6] A thin film (film thickness: 0.851 μm) was obtained in the same manner as in Example 1, except that triethyl citrate (molecular weight: 276) was used as the thermal reorientation accelerator. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating it at 150 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0152] [Example 7] A thin film (film thickness: 0.879 μm) was obtained in the same manner as in Example 2, except that trihexyl O - butyryl citrate (molecular weight: 514) was used as the thermal reorientation accelerator. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating it at 140 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0153] [Example 8] A thin film (film thickness: 0.881 μm) was obtained in the same manner as in Example 1, except that tributyl phosphate (molecular weight: 266) was used as the thermal reorientation accelerator and spin - coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating it at 140 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0154] [Example 9] A thin film (film thickness: 0.867 μm) was obtained in the same manner as in Example 1, except that tris(2 - chloroethyl) phosphate (molecular weight: 285) was used as the thermal reorientation accelerator and spin - coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating it at 140 °C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0155] [Example 10] A thin film (film thickness: 0.902 μm) was obtained in the same manner as in Example 1, except that triamyl phosphate (molecular weight: 308) was used as the thermal reorientation accelerator and spin-coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating at 140°C, a high retardation was exhibited. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0156] [Example 11] A thin film (film thickness: 0.899 μm) was obtained in the same manner as in Example 1, except that triphenyl phosphate (molecular weight: 326) was used as the thermal reorientation accelerator and spin-coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating at 140°C, a high retardation was exhibited. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0157] [Example 12] A thin film (film thickness: 0.945 μm) was obtained in the same manner as in Example 1, except that 2-ethylhexyl diphenyl phosphate (molecular weight: 362) was used as the thermal reorientation accelerator and spin-coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating at 140°C, a high retardation was exhibited. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0158] [Example 13] A thin film (film thickness: 0.879 μm) was obtained in the same manner as in Example 1, except that tri - o - cresyl phosphate (molecular weight: 368) was used as the thermal reorientation accelerator and spin-coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating at 140°C, a high retardation was exhibited. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0159] [Example 14] 4.95 wt% of Polymer 1 and 0.05 wt% of tricresyl phosphate (molecular weight: 368) as a heat reorientation promoting plasticizer were dissolved in 95 wt% of 1,1,1,3,3,3 - hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin - coated at 4000 rpm for 60 seconds, and then dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness 1.022 μm). After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After heating at 140 °C, a high - order phase difference was developed. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0160] [Example 15] A thin film (film thickness 0.911 μm) was obtained in the same manner as in Example 2, except that tricresyl phosphate (molecular weight: 368) was used as a heat reorientation promoting plasticizer and spin - coated at 6000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After heating at 140 °C, a high - order phase difference was developed. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0161] [Example 16] 4 wt% of Polymer 1 and 1 wt% of tricresyl phosphate (molecular weight: 368) as a heat reorientation promoting plasticizer were dissolved in 95 wt% of 1,1,1,3,3,3 - hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin - coated at 5000 rpm for 60 seconds, and then dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness 0.752 μm). After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After heating at 140 °C, a high - order phase difference was developed. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0162] [Example 17] A thin film (film thickness 0.881 μm) was obtained in the same manner as in Example 1, except that tris(2 - butoxyethyl) phosphate (molecular weight: 398) was used as a heat reorientation promoting plasticizer and spin - coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2After irradiation and heating at 140 °C, a high retardation was exhibited. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0163] [Example 18] A thin film (film thickness: 0.901 μm) was obtained in the same manner as in Example 1, except that tris(1,3-dichloro-2-propyl) phosphate (molecular weight: 431) was used as a heat reorientation promoting plasticizer and spin-coated at 4000 rpm. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation and heating at 140 °C, a high retardation was exhibited. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0164] [Example 19] A thin film (film thickness: 0.967 μm) was obtained in the same manner as in Example 1, except that tris(2-ethylhexyl) phosphate (molecular weight: 435) was used as a heat reorientation promoting plasticizer and spin-coated at 4000 rpm. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation and heating at 140 °C, a high retardation was exhibited. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0165] [Example 20] A thin film (film thickness: 0.945 μm) was obtained in the same manner as in Example 2, except that dioctyl 4-cyclohexene-1,2-dicarboxylate (molecular weight: 451) was used as a heat reorientation promoting plasticizer. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation and heating at 140 °C, a high retardation was exhibited. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0166] [Example 21] A thin film (film thickness: 1.113 μm) was obtained in the same manner as in Example 1, except that Adeka Stab P-300 (molecular weight: 3000, adipic acid-based polyester) was used as a heat reorientation promoting plasticizer and spin-coated at 2000 rpm. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2After irradiation, when heated at 140 °C, a high-order phase difference appeared. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0167] [Example 22] A thin film (film thickness: 0.952 μm) was obtained in the same manner as in Example 14, except that Irganox (registered trademark) 245 (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]) (molecular weight: 587) was used as the heat reorientation promoting plasticizer. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation, when heated at 140 °C, a high-order phase difference appeared. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0168] [Example 23] A thin film (film thickness: 0.915 μm) was obtained in the same manner as in Example 1, except that Irganox (registered trademark) 245 (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]) (molecular weight: 587) was used as the heat reorientation promoting plasticizer and spin-coated at 4000 rpm. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation, when heated at 140 °C, a high-order phase difference appeared. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0169] [Example 24] 4.25 wt% of Polymer 1 and 0.75 wt% of Irganox (registered trademark) 245 (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]) (molecular weight: 587) as the heat reorientation promoting plasticizer were dissolved in 95 wt% of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 4000 rpm for 60 seconds, and dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness: 0.936 μm). The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2After irradiation, when heated at 140 °C, a high-order phase difference was manifested. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0170] [Example 25] 4.5 wt% of Polymer 1 and 0.5 wt% of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (molecular weight: 406) as a thermal reorientation promoting plasticizer were dissolved in 95 wt% of a 1,1,1,3,3,3-hexafluoroisopropanol / chloroform = 4 / 1 (weight ratio) solution, and a thin film (film thickness 1.337 μm) was obtained in the same manner as in Example 1 except that spin coating was performed at 2000 rpm. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation, when heated at 140 °C, a high-order phase difference was manifested. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0171] [Example 26] A thin film (film thickness 1.127 μm) was obtained in the same manner as in Example 1 except that spin coating was performed at 2000 rpm using isodecyl phosphite (molecular weight: 503) as a thermal reorientation promoting plasticizer. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation, when heated at 140 °C, a high-order phase difference was manifested. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0172] [Example 27] A thin film (film thickness 1.054 μm) was obtained in the same manner as in Example 1 except that spin coating was performed at 2000 rpm using didodecyl 3,3'-thiodipropionate (molecular weight: 515) as a thermal reorientation promoting plasticizer. The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation, when heated at 140 °C, a high-order phase difference was manifested. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0173] [Example 28] A thin film (film thickness: 0.963 μm) was obtained in the same manner as in Example 14, except that bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight: 509) was used as the heat reorientation promoting plasticizer. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating it at 140°C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0174] [Example 29] A thin film (film thickness: 0.937 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 the heat reorientation promoting plasticizer and spin-coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating it at 140°C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0175] [Example 30] A thin film (film thickness: 1.009 μm) was obtained in the same manner as in Example 24, except that bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (molecular weight: 509) was used as the heat reorientation promoting plasticizer and spin-coated at 4000 rpm. After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating it at 140°C, a high retardation was developed. The retardation amount in terms of a film thickness of 10 μm is shown in Table 1.

[0176] [Example 31] 1.8 wt% of Polymer 1 and 0.2 wt% of tricresyl phosphate (molecular weight: 368) as a heat reorientation promoter were dissolved in 98 wt% of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 6000 rpm for 60 seconds, and then dried in an oven at 60°C for 60 minutes to obtain a thin film (film thickness: 0.2 μm). After irradiating the obtained thin film with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heating it at 130°C, a liquid crystal alignment film was prepared. Two 25-μm-thick PET films (manufactured by Toray Industries, Inc., product name: Lumirror (R) T60) cut to 1.5 mm × 20 mm were used as spacers, and two quartz glass plates on which this liquid crystal alignment film was laminated were overlapped such that the thin films were on the inside and the directions in which polarized ultraviolet light was irradiated were parallel. The periphery of the quartz glass plates excluding the part that would become the liquid crystal injection port area was adhered with an instant adhesive (manufactured by Toagosei Co., Ltd., Aron Alpha 201) to form a liquid crystal empty cell. After adhesion, 4-cyano-4'-pentylbiphenyl heated to 50 °C was injected into the liquid crystal empty cell to form a liquid crystal cell. Regarding the obtained liquid crystal cell, when observed in three directions using a polarizing microscope such that the angle of the polarizer was 0°, 45°, and 90° with respect to the direction in which polarized ultraviolet light was irradiated on the thin film, the microscope images changed to dark, bright, and dark, confirming that the liquid crystal directors were uniformly aligned. Table 2 shows the manufacturability of the liquid crystal alignment film by heat treatment at 200 °C or lower. [In this specification, the liquid crystal director is intended to mean the vector of the direction (orientation principal axis) in which the long axes of liquid crystalline molecules are aligned.]

[0177] [Comparative Example 1] 5% by weight of Polymer 1 was dissolved in 95% by weight of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 6000 rpm for 60 seconds, and dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness: 0.954 μm). When the obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 and then heated at 140 °C, no high retardation was exhibited. Table 1 shows the retardation amount in terms of a film thickness of 10 μm.

[0178] [Comparative Example 2] 4.5% by weight of Polymer 1 and 0.5% by weight of dimethyl phthalate (molecular weight: 194) were dissolved in 95% by weight of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 6000 rpm for 60 seconds, and dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness: 0.856 μm). The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2After irradiation, when heated at 150 °C, no high-order phase difference was observed. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0179] [Comparative Example 3] 4.5% by weight of Polymer 1 and 0.5% by weight of trimethyl phosphate (molecular weight: 140) were dissolved in 95% by weight of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 4000 rpm for 60 seconds, and then dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness 0.867 μm). The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation, when heated at 150 °C, no high-order phase difference was observed. The phase difference amount in terms of a film thickness of 10 μm is shown in Table 1.

[0180] [Comparative Example 4] 2% by weight of Polymer 1 was dissolved in 98% by weight of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast onto a quartz glass substrate and spin-coated at 7000 rpm for 60 seconds, and then dried in an oven at 60 °C for 60 minutes to obtain a thin film (film thickness 0.2 μm). The obtained thin film was irradiated with polarized ultraviolet light of 248 nm at 500 mJ / cm 2 After irradiation, it was heated at 130 °C to prepare a thin film. Two 25-μm-thick PET films (manufactured by Toray, product name: Lumirror (R) T60) cut into 1.5 mm × 20 mm were used as spacers, and two quartz glass plates with this thin film laminated were overlapped so that the thin film was on the inside and the directions of polarized ultraviolet light irradiation were parallel. The periphery of the quartz glass plate excluding the liquid crystal injection port area was adhered with an instant adhesive (manufactured by Toagosei Co., Ltd., Aron Alpha 201) to form a liquid crystal empty cell. After adhesion, 4-cyano-4'-pentylbiphenyl heated at 50 °C was injected into the liquid crystal empty cell to form a liquid crystal cell. Regarding the obtained liquid crystal cell, when observed in three directions using a polarizing microscope so that the angles of the polarizer were 0°, 45°, and 90° with respect to the direction in which the thin film was irradiated with polarized ultraviolet light, the microscope image remained always bright, confirming that the liquid crystal directors were not uniformly aligned. Table 2 shows the manufacturability of the liquid crystal alignment film by heat treatment at 200 °C or lower.

[0181] By irradiating the thin film of Example 31 with polarized ultraviolet light and performing heat treatment at 200°C or lower, its usability as a liquid crystal alignment film becomes more prominent by comparison with Comparative Example 4.

[0182]

Table 1

[0183]

Table 2

Claims

1. A resin composition containing 80 to 99.99% by weight of a polymer having a structural unit A represented by the following formula (1), a structural unit B represented by the following formula (2), and a structural unit C represented by the following formula (3), and 0.01 to 20% by weight of a thermal reorientation accelerator having a molecular weight of 200 or more and 10,000 or less. 【Chemical 1】 (In formula (1), X １ ~X ３ each independently represents an alicyclic hydrocarbon group having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Here, the substituents in X １ ~X ３ each independently represent one kind of the group consisting of a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. When X １ ~X ３ do not have a substituent, they are hydrogen atoms. Y １ and Y ２ represent -O-. Ar １ and Ar ２ each independently represent an aromatic ring having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. Here, the substituents in Ar １ and Ar ２ each independently represent one kind of the group consisting of a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. When Ar １ and Ar ２ do not have a substituent, they are hydrogen atoms.) R １ ~R ４ represents a hydrogen atom. L １ and L ４ represents -O-. L ２ and L ３ represents a single bond. a and b represent 0. ) 【Chemical 2】 (In formula (2), Y ３ and Y ４ represent -O-. X ４ to X ６ each independently represents an aromatic ring having 5 to 7 carbon atoms which may have a substituent, and any carbon atom in the aromatic ring may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom. R １１ and R １２ represent an alkyl group having 1 to 5 carbon atoms. c represents 0 or 1.) 【Chemical Formula 3】 (In formula (3), Y ５ and Y ６ represent -CO-. Z represents an alicyclic hydrocarbon group having 5 to 7 carbon atoms.)

2. Ar in formula (1) １ and Ar ２ The resin composition according to claim 1, wherein １ and ２ are benzene rings which may have substituents.

3. The resin composition according to any one of claims 1 to 2, wherein the thermal reorientation accelerator is a plasticizer.

4. The resin composition according to any one of claims 1 to 2, wherein the thermal reorientation accelerator is an antioxidant.

5. The resin composition according to any one of claims 1 to 2, wherein the thermal reorientation accelerator is a light stabilizer.

6. An optical thin film containing the resin composition according to any one of claims 1 to 5.

7. An optical thin film obtained by irradiating the optical thin film according to claim 6 with ultraviolet light.

8. An optical thin film obtained by irradiating the optical thin film according to claim 7 with polarized ultraviolet light or obliquely incident ultraviolet light.

9. The optical thin film according to claim 7 or claim 8, wherein the photoreaction rate of the photoreactive group is 50% or less.

10. An optical thin film obtained by heating the optical thin film according to any one of claims 7 to 9 at a temperature within the range where the resin composition exhibits liquid crystallinity.

11. A retardation film provided with the thin film according to any one of claims 6 to 10.

12. A liquid crystal alignment film provided with the thin film according to any one of claims 6 to 10.

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