JP2022187901A - Composition of polymer including photoreactive group, optical thin film - Google Patents

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

The present invention relates to compositions of polymers containing photoreactive groups. More particularly, it relates to a polymer composition containing photoreactive groups and a retardation film containing the composition.

Retardation films are used in various image display devices from the viewpoint of widening the viewing angle. As an existing retardation film, it is produced using a polymerizable liquid crystalline compound. At this time, in order to align the polymerizable liquid crystalline compound, it is necessary to provide an alignment film on the support forming the optically anisotropic layer, and an alignment film subjected to rubbing treatment or photo-alignment treatment is used. (See Patent Documents 1 to 3, for example). However, both of them require complicated manufacturing equipment and processes, and have problems in product yield. In addition, an optical thin film and a retardation film exhibiting a retardation Re/thickness of 100 nm or more by using a side chain type liquid crystal acrylate resin containing a photoreactive group, without the need for an alignment film, by irradiating polarized ultraviolet rays and heat treatment. are proposed (for example, Patent Documents 4 and 5). However, side chain type liquid crystal acrylate resins containing photoreactive groups have problems such as high cost due to multistage synthesis of monomers and low heat resistance. Linear liquid crystalline polyester resins containing photoreactive groups do not require an alignment film and can be used to form optical thin films and retardation films by irradiating polarized ultraviolet rays and heat treatment. Production of retardation films can be expected. However, although linear liquid crystalline polyester resins have excellent heat resistance, there is a problem that high processing temperatures of 200° C. or higher are required (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, polyethylene terephthalate (heat resistant temperature about 160 ° C.), polyethylene terenaphthalate (heat resistant temperature about 200 ° C.), cycloolefin polymer ( There is a problem that inexpensive general-purpose resin film supporting substrates such as heat resistant temperature of about 160° C. cannot be used.

Japanese Patent Laid-Open No. 8-160430 Special table 2003-505561 International Publication No. 2010-150748 JP 2002-226858 International Publication No. 2014-017497 JP 2018-188529 JP 2021-028375 JP 2021-028384

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

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, and is a general-purpose resin film. The inventors have found that the thermal reorientation of the polymer is promoted at a heat treatment temperature lower than the heat-resistant temperature of the support substrate, making it possible to manufacture the polymer on a general-purpose resin film support substrate, and have completed the present invention.

That is, one embodiment of the present invention has a structural unit A represented by the following formula (1), and a structural unit B represented by the following formula (2) or represented by the following formula (3) 80 to 99.99% by weight of a polymer having at least one structural unit C among is.

(In Formula (1), X ₁ to X ₃ are each independently an optionally substituted C 5 to 7 aromatic ring or an optionally substituted C 5 to 7 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. ₁ to X ₃ each independently represents one 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 X ₁ to X ₃ are substituents is a hydrogen atom, Y ₁ and Y ₂ each independently represent one member of the group consisting of —O—, —CO—, and —NR ₉ —, where R ₉ is hydrogen represents one member of the group consisting of an atom or an alkyl group having 1 to 5 carbon atoms, Ar ₁ and Ar ₂ each independently represent an optionally substituted aromatic ring having 5 to 7 carbon atoms, Any carbon atom in the aromatic ring may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom, wherein the substituents in Ar ₁ and Ar ₂ are each independently a halogen atom, a C 1-5 represents one member of the group consisting of an alkyl group and an alkoxy group having 1 to 5 carbon atoms, and represents a hydrogen atom when Ar ₁ and Ar ₂ have no substituents, and R ₁ to R ₄ each independently represents one 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, and L ₁ and L ₄ are a single bond or —O -, -NR ₅ -, wherein R ₅ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L ₂ and L ₃ each represent a single bond or —O—, —CO—O—, —CO—NR ₆ —, —CO—, —CR ₇ R ₈ —, wherein R ₆ is a hydrogen atom or has 1 to 1 carbon atoms. represents one of the group consisting of an alkyl group of 5. R ₇ and R ₈ each independently represent one 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 represents 0 or 1.)

(In formula (2), Y ₃ and Y ₄ each independently represent one member of the group consisting of —O—, —CO—, and —NR ₁₀ —, where R ₁₀ is a hydrogen atom or the number of carbon atoms represents one member of the group consisting of alkyl groups of 1 to 5. X ₄ to X ₆ each independently have an optionally substituted aromatic ring having 5 to 7 carbon atoms or a substituent; any carbon atom in the aromatic ring or in the alicyclic hydrocarbon group is substituted with a nitrogen atom, an oxygen atom, or a sulfur atom R ₁₁ and R ₁₂ each represent one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c represents 0 or 1.)

(In formula (3), Y ₅ and Y ₆ each independently represent one member of the group consisting of —O—, —CO— and —NR ₁₃ —, where R ₁₃ is a hydrogen atom or a carbon number represents one of the group consisting of alkyl groups of 1 to 5. Z is an alicyclic hydrocarbon group of 5 to 7 carbon atoms, a linear alkylene group of 2 to 20 carbon atoms, It represents one of the group consisting of branched alkylene groups.)

Another aspect of the present invention relates to an optical thin film containing the composition.

Another aspect of the present invention relates to a retardation film including the thin film.

Furthermore, another aspect of the present invention relates to a liquid crystal alignment film including the thin film.

According to the present invention, since a high retardation is exhibited even at a heat treatment temperature of 200 ° C. or less, a composition exhibiting reactivity to ultraviolet light that can be formed on a general-purpose resin substrate, an optical thin film, and a retardation film comprising the same can be provided.

The composition that is one embodiment of the present invention is described in detail below.

As one embodiment of the present invention, a structure having a structural unit A represented by the following formula (1) and a structural unit B represented by the following formula (2) or a structure represented by the following formula (3) A composition containing 80 to 99.99% by weight of a polymer having at least one type of unit C and 0.01 to 20% by weight of a thermal reorientation accelerator having a molecular weight of 200 or more and 10000 or less (hereinafter referred to as "the present (referred to as "composition of the invention").

(In Formula (1), X ₁ to X ₃ are each independently an optionally substituted C 5 to 7 aromatic ring or an optionally substituted C 5 to 7 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. ₁ to X ₃ each independently represents one 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 X ₁ to X ₃ are substituents is a hydrogen atom, Y ₁ and Y ₂ each independently represent one member of the group consisting of —O—, —CO—, and —NR ₉ —, where R ₉ is hydrogen represents one member of the group consisting of an atom or an alkyl group having 1 to 5 carbon atoms, Ar ₁ and Ar ₂ each independently represent an optionally substituted aromatic ring having 5 to 7 carbon atoms, Any carbon atom in the aromatic ring may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom, wherein the substituents in Ar ₁ and Ar ₂ are each independently a halogen atom, a C 1-5 represents one member of the group consisting of an alkyl group and an alkoxy group having 1 to 5 carbon atoms, and represents a hydrogen atom when Ar ₁ and Ar ₂ have no substituents, and R ₁ to R ₄ each independently represents one 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, and L ₁ and L ₄ are a single bond or —O -, -NR ₅ -, wherein R ₅ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and L ₂ and L ₃ each represent a single bond or —O—, —CO—O—, —CO—NR ₆ —, —CO—, —CR ₇ R ₈ —, wherein R ₆ is a hydrogen atom or has 1 to 1 carbon atoms. represents one of the group consisting of an alkyl group of 5. R ₇ and R ₈ each independently represent one 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 represents 0 or 1.)

(In formula (2), Y ₃ and Y ₄ each independently represent one member of the group consisting of —O—, —CO—, and —NR ₁₀ —, where R ₁₀ is a hydrogen atom or the number of carbon atoms represents one member of the group consisting of alkyl groups of 1 to 5. X ₄ to X ₆ each independently have an optionally substituted aromatic ring having 5 to 7 carbon atoms or a substituent; any carbon atom in the aromatic ring or in the alicyclic hydrocarbon group is substituted with a nitrogen atom, an oxygen atom, or a sulfur atom R ₁₁ and R ₁₂ each represent one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c represents 0 or 1.)

(In formula (3), Y ₅ and Y ₆ each independently represent one member of the group consisting of —O—, —CO— and —NR ₁₃ —, where R ₁₃ is a hydrogen atom or a carbon number represents one of the group consisting of alkyl groups of 1 to 5. Z is an alicyclic hydrocarbon group of 5 to 7 carbon atoms, a linear alkylene group of 2 to 20 carbon atoms, It represents one of the group consisting of branched alkylene groups.)

In formula (1), X ₁ to X ₃ are each independently an optionally substituted C 5 to 7 aromatic ring or an optionally substituted C 5 to 7 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, examples of substituents for X ₁ to X ₃ include halogen atoms, alkyl groups having 1 to 5 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms, and X ₁ to X ₃ have no substituents. is a hydrogen atom. X ₁ to X ₃ are preferably one selected from the group consisting of benzene ring, methylbenzene ring, t-butylbenzene ring, dimethylbenzene ring, tetrafluorobenzene ring and cyclohexane ring, more preferably trans-cyclohexane ring. be.

Y ₁ and Y ₂ each independently represent one member of the group consisting of -O-, -CO- and -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-.

Ar ₁ and Ar ₂ each independently represent an optionally substituted aromatic ring having 5 to 7 carbon atoms, and any carbon atom in the aromatic ring is a nitrogen atom, an oxygen atom or a sulfur atom. may be substituted. Examples of substituents for Ar ₁ and Ar ₂ include halogen atoms, alkyl groups having 1 to 5 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms, and Ar ₁ and Ar ₂ have no substituents. is a hydrogen atom. Ar ₁ and Ar ₂ are preferably an optionally substituted benzene ring, more preferably a benzene ring.

R ₁ to 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. R ₁ to R ₄ are preferably hydrogen atoms or cyano groups, more preferably hydrogen atoms.

L ₁ and L ₄ each independently represent a single bond or one of the group consisting of -O- and -NR ₅ -. L ₁ and L ₄ are preferably -O- or -NR ₅ -. R ₅ in L ₁ and L ₄ represents one member 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 for R ₅ include methyl group, ethyl group, propyl group, butyl group and pentyl group.

L ₂ and L ₃ each independently represent a single bond or one member of the group consisting of -O-, -CO-O-, -CO-NR ₆ -, -CO- and -CR ₇ R ₈ -. However _, the left _- right relationship of L2 and L3 may be reversed. L ₂ and L ₃ are preferably a single bond or -CO-NR ₆ -, more preferably a single bond. R ₆ in L ₂ and L ₃ represents one member 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 for R ₆ include methyl group, ethyl group, propyl group, butyl group and pentyl group. R ₇ and R ₈ in L ₂ and L ₃ each independently represent one member of the group consisting of a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. Halogen atoms for R ₇ and R ₈ include fluorine, chlorine, bromine and iodine atoms. Examples of the alkyl group having 1 to 5 carbon atoms for R ₇ and R ₈ include methyl group, ethyl group, propyl group, butyl group and pentyl group.

a and b each independently represent 0 or 1;

In formula (2), Y ₃ and Y ₄ each independently represent one member of the group consisting of -O-, -CO- and -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. Y ₃ and Y ₄ are preferably -O- or -CO-.

X ₄ to X ₆ are each independently an optionally substituted aromatic ring having 5 to 7 carbon atoms or an optionally substituted alicyclic hydrocarbon group having 5 to 7 carbon atoms 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. Examples of substituents for X ₄ to X ₆ include halogen atoms, alkyl groups having 1 to 5 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms, and X ₄ to X ₆ have no substituents. is a hydrogen atom. X ₄ to X ₆ are preferably one selected from the group consisting of benzene ring, methylbenzene ring, t-butylbenzene ring, dimethylbenzene ring, tetrafluorobenzene ring or cyclohexane ring, more preferably benzene ring or trans- It is a cyclohexane ring.

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. Examples of the alkyl group having 1 to 5 carbon atoms for R ₅ include methyl group, ethyl group, propyl group, butyl group and pentyl group.

c represents 0 or 1;

In formula (3), Y ₅ and Y ₆ each independently represent one member of the group consisting of -O-, -CO- and -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. Y ₅ and Y ₆ are preferably -CO-.

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. Z is preferably an alicyclic hydrocarbon group having 5 to 7 carbon atoms or a linear alkylene group having 2 to 20 carbon atoms, more preferably an alicyclic hydrocarbon group having 5 to 7 carbon atoms, carbon It is a linear alkylene group of number 2 to 10.

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

(In formula (4), X ₇ and X ₈ are each independently an optionally substituted C 5-7 aromatic ring or an optionally substituted C 5-7 L ₅ is a single bond or the group consisting of —O—, —CO—O—, —CO—NR ₁₆ —, —CO—, —CR ₁₇ R ₁₈ — wherein R ₁₆ represents either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₁₇ and R ₁₈ each independently represent a hydrogen atom, a halogen atom, or a C 1 to represents one of the group consisting of alkyl groups of 5. m and l each independently represent 0 or 1. R ₁₄ and R ₁₅ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a carbon number represents one of the group consisting of an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and n ₁ and n ₂ each independently represents an integer of 0 to 4.)

(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.)

In the copolymer contained in the composition of the present invention, structural unit A1 is preferably structural unit _A2 represented by the following formula ( ₆ ).

(In formula (6), Y ₇ represents one member of the group consisting of optionally substituted benzene ring, biphenyl ring, cyclohexane ring, and bicyclohexane ring. R ₁₄ and R ₁₅ each independently represents 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 of 0 to 4; )

The method for synthesizing the copolymer contained in the composition of the present invention is not particularly limited, and it is synthesized by a polymerization method known in the art, for example, a melt polymerization method or a solution polymerization method using a corresponding dicarboxylic acid chloride. be. Among these, a solution polymerization method capable of polymerization under mild conditions is particularly preferable. The seeds may be interfacially polycondensed.

A polymer that does not contain the structural unit A represented by the formula (1) does not undergo a photoreaction, so that a thin film made of the polymer is excellent even when subjected to polarized ultraviolet irradiation or oblique incident ultraviolet irradiation and heat treatment. It does not exhibit liquid crystal orientation.

Since the 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, it is subjected to polarized ultraviolet irradiation or oblique incident ultraviolet irradiation and heat treatment. However, the thin film made of the polymer does not exhibit excellent liquid crystal orientation.

The composition of the present invention contains a thermal reorientation promoter. The optical thin film and the retardation film obtained using the composition of the present invention have improved molecular mobility due to the thermal reorientation accelerator. A reorientation treatment becomes possible.

The thermal reorientation promoter contained in the composition of the present invention has a molecular weight of 200 or more and 10,000 or less. If the molecular weight is less than 200, the problem of deposition and exudation of the additive in a high-temperature environment, or the problem of volatilization of the additive in a high-temperature environment occurs, and the performance as an optical thin film cannot be maintained. When the molecular weight is more than 10,000, the improvement efficiency of polyester molecular orientation is poor. It is more preferable that the thermal reorientation accelerator of the present invention is 300 or more and 10000 or less because of its low volatility during heat treatment.

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. From the viewpoint of precipitation and exudation of the thermal reorientation accelerator in a high temperature environment, more preferably 85 to 99.9% by weight of the polymer and 0.1 to 15% by weight of the thermal reorientation accelerator, from the viewpoint of thermal reorientation acceleration efficiency. Particularly preferably, 85 to 99.0% by weight of polymer and 1.0 to 15% by weight of thermal reorientation accelerator. In the present invention, when the proportion of the thermal reorientation accelerator is less than 0.01% by weight, it becomes difficult to promote thermal reorientation, and when it exceeds 20% by weight, the thermal reorientation accelerator tends to precipitate or exude. .

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

Examples of plasticizers include carboxylic acid esters, phosphoric acid esters, polymer plasticizers, and the like.

Specific examples of carboxylic acid esters include phthalates, trimellitates, pyromellitic esters, citrates, oleates, ricinoleates, sebacates, stearates, adipates, and epoxidized esters. can be mentioned.

Specific examples of polymer plasticizers include polyester plasticizers and polyether plasticizers.

The thermal reorientation accelerator of the present invention is preferably a plasticizer.

The phthalate used as the thermal reorientation accelerator of the present invention refers to one having a molecular weight of 200 or more and 10,000 or less including a structure represented by the following formula (7).

(In formula (7), R ₁₉ and R ₂₀ each independently represent 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. Represents one selected from the group consisting of rings, which may have either a substituent or an unsaturated bond.R ₁₉ and R ₂₀ are each independent of each other due to low volatility during heat treatment In addition, it is preferable that the number of carbon atoms is 2 or more.)

The trimellitate used 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 including the structure represented by the following formula (8).

(In formula (8), R ₂₁ to R ₂₃ each independently represent 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. represents one selected from the group consisting of rings, which may have either a substituent or an unsaturated bond.)

Pyromellitic acid ester, which is exemplified 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 including the structure represented by the following formula (9).

(In formula (9), R ₂₄ to R ₂₇ each independently represent 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. represents one selected from the group consisting of rings, which may have either a substituent or an unsaturated bond.)

The citric acid ester, which is exemplified 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 including the structure represented by the following formula (10).

(In formula (10), R ₂₈ to R ₃₀ each independently represent 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. represents one selected from the group consisting of rings, which may have either a substituent or an unsaturated bond, R ₃₁ is a hydrogen atom, an acetyl group having 1 to 20 carbon atoms, represents one selected from the group consisting of 1 to 20 alkyl groups, alicyclic hydrocarbons, aromatic rings, heterocyclic rings, polycyclic aromatic rings, or condensed aromatic rings, and these are substituents, unsaturated may have any of the bonds.)

The oleic ester used 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 including the structure represented by the following formula (11).

(In formula (11), R ₃₂ is 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. represents one type, and these may have either a substituent or an unsaturated bond.)

The ricinoleic ester used 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 including the structure represented by the following formula (12).

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

The sebacic acid ester, which is exemplified 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 including the structure represented by the following formula (13).

(In formula (13), R ₃₅ and R ₃₆ are each independently 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. represents one selected from the group consisting of rings, which may have either a substituent or an unsaturated bond.)

The stearate used as the thermal reorientation accelerator of the present invention refers to one having a molecular weight of 200 or more and 10,000 or less including a structure represented by the following formula (14).

(In formula (14), R ₃₇ is 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. represents one type, and these may have either a substituent or an unsaturated bond.)

The adipic acid ester, which is exemplified 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 including the structure represented by the following formula (15).

(In formula (15), R ₃₈ and R ₃₉ each independently represent 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. represents one selected from the group consisting of rings, which may have either a substituent or an unsaturated bond, and from low volatility during heat treatment, R ₃₈ and R ₃₉ are each independently In addition, it is preferable that the number of carbon atoms is 2 or more.)

The epoxidized ester that can be used as the thermal reorientation accelerator of the present invention 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. Cyclohexane-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 , epoxidized fatty acid 2-ethylhexyl, and the like.

Phosphate esters include compounds represented by the following formula (16).

(In formula (16), R ₄₀ to R ₄₂ each independently represent 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. represents one selected from the group consisting of rings, which may have either a substituent or an unsaturated bond, and from the low volatility during heat treatment, R ₄₀ to R ₄₂ are each independently In addition, it is preferable that the number of carbon atoms is 3 or more.)

The polyester plasticizer that can be used as the thermal reorientation accelerator of the present invention is a polymer containing a structural unit represented by the following formula (17) and has a molecular weight of 200 or more and 10,000 or less.

(In formula (17), R ₄₃ and R ₄₄ are each independently 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. represents one selected from the group consisting of rings, which may have either a substituent or an unsaturated bond.)

The polyether plasticizer that can be used as the thermal reorientation accelerator of the present invention is a polymer containing a structural unit represented by the following formula (18) and has a molecular weight of 200 or more and 10,000 or less.

(In formula (18), R ₄₅ is 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. represents one type, and these may have either a substituent or an unsaturated bond.)

Examples of antioxidants include phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, lactone antioxidants, hydroxylamine antioxidants, and vitamin E antioxidants. antioxidants, and other antioxidants.

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

The phenolic antioxidant, which is exemplified 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 including a structure represented by the following formula (19).

(In formula (19), at least one of R ₅₀ and R ₅₁ is 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, represents one selected from the group consisting of an alicyclic hydrocarbon, an aromatic ring, a polycyclic aromatic ring, or a condensed aromatic ring, even if they have either a substituent or an unsaturated bond Well, the other is 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, or a polycyclic aromatic ring. , or one selected from the group consisting of condensed aromatic rings, which may have either a substituent or an unsaturated bond.These structures are not particularly limited, but are available _tert - _butyl group is particularly preferable from the viewpoint of represents one selected from the group consisting of a ring, a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, which may have either a substituent or an unsaturated bond.)

Phenolic antioxidants that can be used as thermal reorientation accelerators of the present invention are not limited to those represented by formula (19), and examples include galvinoxyl free radicals, 3,3′,5,5′-tetra -tert-butyl-4,4'-stilbenequinone, 4-(hexyloxy)-2,3,6-trimethylphenol and the like.

The amine-based antioxidant that is exemplified 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 containing a structure represented by the following formula (20).

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

The amine-based antioxidant that can be used as the thermal reorientation accelerator of the present invention is not limited to those represented by formula (20). Also included are quinoline, poly(2,2,4-trimethyl-1,2-dihydroquinoline) and the like.

The phosphorus-based antioxidant that can be used 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 containing a structure represented by the following formula (21).

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

The sulfur-based antioxidant that is exemplified 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 containing a structure represented by the following formula (22).

(In formula (22), R ₅₅ is 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. These may have either a substituent or an unsaturated bond, and R ₅₆ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon, an aromatic ring, represents one selected from the group consisting of a heterocyclic ring, a polycyclic aromatic ring, or a condensed aromatic ring, which may have either a substituent or an unsaturated bond. R ₅₅ and R ₅₆ each independently preferably have 6 or more carbon atoms because of low volatility.)

Light stabilizers include, for example, hindered amine light stabilizers.

The thermal reorientation promoter of the present invention is preferably a light stabilizer.

The hindered amine-based light stabilizer, which is exemplified as the thermal reorientation accelerator of the present invention, refers to those having a structural unit represented by the following formula (23) and having a molecular weight of 200 or more and 10,000 or less.

(In formula (23), Y ₈ represents one member of the group consisting of —O—, —CO—, and —NR ₅₇ —, wherein R ₅₇ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Each of R ₅₈ to R ₆₁ independently represents 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 ring represents one selected from the group consisting of aromatic rings, which may have either a substituent or an unsaturated bond, and among these, a methyl group is particularly preferred from the viewpoint of availability.R ₆₂ is 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 represents one selected from the group, and may have either a substituent or an unsaturated bond.)

Among these various additives, the plasticizer is preferable because it is readily available, has good compatibility with the resin, and is particularly excellent in promoting thermal reorientation after being added to the resin. These thermal reorientation accelerators may be used singly or in combination of two or more.

The thermal reorientation accelerator of the present invention, in addition to the purpose of improving the thermal reorientation property, improves mechanical properties, imparts flexibility, imparts water absorption resistance, reduces water vapor transmission rate, improves thermal stability, and improves weather resistance. It may be added for purposes such as

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

The resin composition of the present invention can be obtained by blending a polyester resin having a photoreactive group and a thermal reorientation accelerator (hereinafter referred to as resin or the like).

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

The composition of the present invention may contain other polymers, crystal nucleating agents, surfactants, polymer electrolytes, conductive complexes, inorganic fillers, pigments, antistatic agents, antiblocking agents, A lubricant or the like may be blended.

The composition of the present invention can be used in the form of a thin film. As a result, optical properties are exhibited, and the film can be used as an optical thin film (hereinafter referred to as "thin film of the present invention"). The method for producing the thin film is not particularly limited, and examples thereof include methods such as a melt film-forming method and a solution casting method.

(Melt film-forming method)
The method of melt film formation specifically includes a melt extrusion method using a T-die, a calendar molding method, a hot press method, a co-extrusion method, a co-melting method, a multi-layer extrusion method, an inflation molding method, and the like. Not limited.

(Solution casting method)
The solution casting method is a method in which a solution of a composition dissolved in a solvent (hereinafter referred to as "casting dope") is cast on a supporting substrate, and then the solvent is removed by heating or the like to obtain a thin film. . At that time, methods for casting the casting dope onto the supporting substrate include spin coating, T-die method, doctor blade method, bar coater method, and roll coater method. , a lip coater method, or the like is used. Particularly industrially, the most common method is to continuously extrude the casting dope from a die onto a belt-like or drum-like supporting substrate. Examples of supporting substrates that can be used include glass substrates, metal substrates such as stainless steel and ferrotype, films of polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polyimide, and the like.

The optical thin film using the thin film of the present invention preferably has a thickness of 0.01 to 20 μm from the viewpoint of suitability for thinning optical members, and particularly preferably 1 to 20 μm from the viewpoint of film thickness yield.

(Surfactant)
The thin film of the present invention may contain at least one or more surfactants in order to reduce film thickness unevenness. Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like can be mentioned, and fluorine-containing surfactants are particularly preferred.

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

The thin film of the present invention develops a retardation when irradiated with ultraviolet rays. The UV light may be polarized UV light or oblique incident UV light. At this time, the wavelength of the ultraviolet rays 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 particularly preferably 10 mJ/cm ² or more and 5000 mJ/cm ² or less from the viewpoint of productivity.

The thin film of the present invention is further subjected to heat treatment after the ultraviolet irradiation. This produces a phase difference. From the viewpoint of heat resistance of the resin film supporting substrate, the heat treatment temperature is preferably 50° C. or higher and 200° C. or lower.

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

The retardation properties of the optical thin film using the thin film of the present invention differ depending on the target retardation film. is 80 nm or more, more preferably 100 to 10000 nm, particularly preferably 100 to 5000 nm. The retardation characteristics at this time are measured using an automatic sample tilt type birefringence meter (manufactured by AXOMETRICS, trade name: AxoScan) under the condition of a measurement wavelength of 589 nm.
Re=(ny−nx)×d(A)
(In the formula, nx indicates the refractive index in the in-plane fast axis direction, ny indicates the in-plane refractive index in the slow axis direction, and d indicates the thickness.)

Since the thin film of the present invention exhibits retardation, 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. The film laminated on the thin film of the present invention may be the thin film of the present invention, or may be a polymerizable liquid crystal film, sputtered film, polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polyimide, or other resin film.

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

EXAMPLES 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.

<Measurement of nuclear magnetic resonance spectrum>
A ¹ H-NMR spectrum was measured using a nuclear magnetic resonance apparatus (manufactured by JEOL, trade name: ECZ 400S).

<Polarized UV irradiation>
Ultraviolet rays were irradiated using a mercury light source (manufactured by Asahi Spectrosco, trade name: REX-250) incorporating a bandpass filter (248 nm). When polarized ultraviolet rays were irradiated, only P-polarized light was irradiated using a polarizing beam splitter with a corresponding wavelength.

<Heat treatment>
Heat treatment was performed using either a non-oxidizing atmosphere constant temperature inert oven (manufactured by ESPEC, trade name: IPHH-202).

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

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

<Observation with a polarizing microscope>
Using a microscope (manufactured by Olympus, trade name: BX53), a polarizing condenser (manufactured by Olympus, trade name: U-POC-2), and an analyzer (manufactured by Olympus, trade name: U-AN360P-2), Molecular liquid crystals were observed, and liquid crystal orientation was observed.

<Synthesis Example 1>
Chinese Journal of chemistry, 23, 1523, 2005. tetrahydropyranyl-coumaric acid (10 g, 40.3 mmol) and trans-cyclohexanediol (2.29 g, 19.7 mmol) with the phenol moiety protected, and 4-dimethylaminopyridine (2. 5 g) was dissolved in dry dichloromethane (100 ml) at 0° C. under a stream of nitrogen. To this, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (8.49 g, 44.3 mmol) was added and allowed to react overnight after returning to room temperature. 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 2 hours. The precipitate was filtered to obtain compound 1 6.74 g. The results of ¹ H-NMR spectrum are shown below.
¹ H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 7.53-7.49 (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)

<Synthesis Example 2>
A mixture of 4-methoxy-N-methylaniline (3.00 g, 21.9 mmol), tetrahydrofuran (20 mL) and water (20 mL) was ice-cooled under a nitrogen stream, and then sodium hydrogen carbonate (11 g) was added. A solution of terephthaloyl chloride (2.17 g, 10.7 mmol) in tetrahydrofuran (20 mL) was slowly added to the stirred mixture, and the mixture was stirred under ice cooling for 3 hours. Water (500 mL) was added to the reaction mixture, the resulting solid was collected by filtration, and washed with 2N hydrochloric acid (200 mL) and methanol (300 mL) to give N,N'-bis(4-methoxyphenyl)-N, N'-dimethyl-1,4-benzenedicarboxamide (3.91 g, yield: 90%) was obtained. The results of ¹ H-NMR spectrum are shown below.
¹ H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 7.07 (s, 4H), 6.83 (d, J = 8.0 Hz, 4H), 6.67 (d, J = 8.0 Hz , 4H), 3.73(s, 6H), 3.38(s, 6H).
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). After that, a 1 mol/L boron tribromide dichloromethane solution (7.4 mL) was added over 5 minutes under ice-cooling. After warming the reaction system to room temperature, it was stirred for 15 hours, and the reaction mixture was added to ice-cooled water (300 mL). The solid produced in the system was collected by filtration and washed with water (500 mL) to obtain compound 2 as a brown solid (776 mg, 83%). The results of ¹ H-NMR spectrum are shown below.
¹ H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.55-9.28 (br, 2H), 6.98 (s, 4H), 6.87-6.67 (m, 4H), 6.58-6.49 (m, 4H), 3.20 (s, 6H).
(Compound 2)

<Synthesis Example 3>
Ion-exchanged water (18.5 mL) 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 (0.24 g, 3.29 mmol) were added. 300 g, 7.50 mmol) was dissolved and stirred. A 2.0% by weight aqueous solution (1.5 mL) of tetra-n-butylammonium bromide was added as a catalyst, and the inside of the apparatus was replaced with nitrogen. A solution of compound 3 (0.773 g, 3.70 mmol) dissolved in chloroform (18.5 mL) was placed in a dropping funnel and added dropwise, followed by stirring at room temperature for 3 hours. The solution after the reaction was poured into methanol, and the precipitate was filtered off and dried in vacuum to obtain polymer 1 (yield 88%).
(Compound 3)

[Example 1]
4.5% by weight of polymer 1 and 0.5% by weight of dibutyl phthalate (molecular weight: 278) as a thermal reorientation accelerator to 95% by weight of 1,1,1,3,3,3-hexafluoroisopropanol Dissolved. This was cast on 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: 0.847 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 150° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 2]
5.0% by weight of polymer 1, 0.56% by weight of ditridecyl phthalate (molecular weight: 531) as a thermal reorientation accelerator, and 94.44% by weight of 1,1,1,3,3,3-hexafluoroisopropanol dissolved to %. This was cast on 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: 0.941 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 150° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 6]
A thin 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 promoter. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 150° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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 promoter. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 8]
A thin 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 a thermal reorientation accelerator and spin-coated at 4000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 9]
A thin 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 a thermal reorientation accelerator and spin-coated at 4000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 10]
A thin 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 a thermal reorientation accelerator and spin-coated at 4000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 11]
A thin 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 a thermal reorientation accelerator and spin-coated at 4000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 12]
A thin film (thickness: 0.945 μm) was obtained in the same manner as in Example 1, except that 2-ethylhexyldiphenyl phosphate (molecular weight: 362) was used as a thermal reorientation accelerator and spin-coated at 4000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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 a thermal reorientation accelerator and spin-coated at 4000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 14]
4.95% by weight of polymer 1 and 0.05% by weight of tricresyl phosphate (molecular weight: 368) as a thermal reorientation promoting plasticizer and 95% by weight of 1,1,1,3,3,3-hexafluoroisopropanol dissolved in This was cast on a quartz glass substrate, spin-coated at 4000 rpm for 60 seconds, and dried in an oven at 60° C. for 60 minutes to obtain a thin film (thickness: 1.022 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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 thermal reorientation promoting plasticizer and spin-coated at 6000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 16]
4% by weight of Polymer 1 and 1% by weight of tricresyl phosphate (molecular weight: 368) as a thermal reorientation promoting plasticizer were dissolved in 95% by weight of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast on 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: 0.752 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 17]
A thin 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 thermal reorientation-promoting plasticizer and spin-coated at 4000 rpm. rice field. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 18]
A thin film (thickness 0 .901 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 19]
A thin 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 thermal reorientation promoting plasticizer and spin-coated at 4000 rpm. . When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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 the thermal reorientation promoting plasticizer. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 21]
A thin film (thickness: 1.113 μm) was formed in the same manner as in Example 1 except that Adekasizer P-300 (molecular weight: 3000, adipic acid-based polyester) was used as a thermal reorientation promoting plasticizer and spin coating was performed at 2000 rpm. Obtained. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 22]
Irganox® 245 (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]) as a thermal reorientation promoting plasticizer (molecular weight: 587 ) was used in the same manner as in Example 14 to obtain a thin film (thickness: 0.952 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 23]
Irganox® 245 (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)]) as a thermal reorientation promoting plasticizer (molecular weight: 587 ) was used to obtain a thin film (thickness: 0.915 μm) in the same manner as in Example 1, except that spin coating was performed at 4000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 24]
4.25% by weight of Polymer 1 and Irganox® 245 (bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis (oxyethylene)]) (molecular weight: 587) was dissolved in 95% by weight of 1,1,1,3,3,3-hexafluoroisopropanol. This was cast on a quartz glass substrate, spin-coated at 4000 rpm for 60 seconds, and dried in an oven at 60° C. for 60 minutes to obtain a thin film (thickness: 0.936 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 25]
4.5% by weight of polymer 1 and 0.5% by weight of 4,4′-bis(α,α-dimethylbenzyl)diphenylamine (molecular weight: 406) as a thermal reorientation promoting plasticizer, 1,1,1, A thin film (thickness: 1.337 μm) was prepared in the same manner as in Example 1 except that it was dissolved in 95% by weight of a 3,3,3-hexafluoroisopropanol/chloroform = 4/1 (weight ratio) solution and spin-coated at 2000 rpm. got When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 26]
A thin film (film thickness: 1.127 μm) was obtained in the same manner as in Example 1, except that isodecyl phosphite (molecular weight: 503) was used as a thermal reorientation promoting plasticizer and spin-coated at 2000 rpm. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 27]
A thin film (film thickness: 1.054 μm) was formed in the same manner as in Example 1, except that didodecyl 3,3′-thiodipropionate (molecular weight: 515) was used as a thermal reorientation promoting plasticizer and spin-coated at 2000 rpm. Obtained. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 28]
A thin film (thickness: 0 .963 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[Example 29]
The procedure was the same 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-promoting plasticizer and spin-coated at 4000 rpm. A thin film (thickness: 0.937 μm) was obtained. When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., a high retardation was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

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

[Example 31]
1.8% by weight of polymer 1 and 0.2% by weight of tricresyl phosphate (molecular weight: 368) as a thermal reorientation accelerator to 98% by weight of 1,1,1,3,3,3-hexafluoroisopropanol Dissolved. This was cast on 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 resulting thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 130° C. to form a liquid crystal alignment film.
Two pieces of 25 μm thick PET film (manufactured by Toray, product name: Lumirror (R) T60) cut into 1.5 mm×20 mm pieces were used as spacers, and two pieces of quartz glass plates laminated with this liquid crystal alignment film were placed on the inner side of the thin film. , and superimposed so that the direction in which the polarized ultraviolet light is irradiated is parallel, and adheres to the periphery of the quartz glass plate except for the part that will be the liquid crystal injection port area with an instant adhesive (Aron Alpha 201, manufactured by Toagosei Co., Ltd.). A liquid crystal empty cell was used. After bonding, 4-cyano-4′-pentylbiphenyl heated at 50° C. was injected into the empty liquid crystal cell to form a liquid crystal cell. The resulting liquid crystal cell was observed using a polarizing microscope in three directions 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. changed from dark to bright to dark, confirming that the liquid crystal directors were uniformly oriented. Table 2 shows whether or not a liquid crystal alignment film can be manufactured by heat treatment at 200° C. or less.
[In this specification, the liquid crystal director means a vector in the direction in which the long axes of the liquid crystalline molecules are aligned (main axis of alignment). ]

[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 on 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: 0.954 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 140° C., no high phase difference was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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 on 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: 0.856 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 150° C., no high phase difference was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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 on a quartz glass substrate, spin-coated at 4000 rpm for 60 seconds, and dried in an oven at 60° C. for 60 minutes to obtain a thin film (thickness: 0.867 μm). When the obtained thin film was irradiated with 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 150° C., no high phase difference was developed. Table 1 shows the retardation amount in terms of film thickness of 10 μm.

[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 on 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 500 mJ/cm ² of polarized ultraviolet light of 248 nm and then heated at 130° C. to form a thin film.
Two sheets of 25 μm thick PET film (manufactured by Toray, product name: Lumirror (R) T60) cut to 1.5 mm×20 mm were used as spacers, and two quartz glass plates laminated with this thin film were placed on the inner side of the thin film. In addition, they are superimposed so that the direction in which the polarized ultraviolet light is irradiated is parallel, and the liquid crystal space is adhered to the periphery of the quartz glass plate excluding the part that will be the liquid crystal injection port area with an instant adhesive (Aron Alpha 201, manufactured by Toagosei Co., Ltd.). cell. After bonding, 4-cyano-4′-pentylbiphenyl heated at 50° C. was injected into the empty liquid crystal cell to form a liquid crystal cell. The resulting liquid crystal cell was observed using a polarizing microscope in three directions 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. remained bright at all times, confirming that the liquid crystal directors were not uniformly aligned. Table 2 shows whether or not a liquid crystal alignment film can be manufactured by heat treatment at 200° C. or less.

A comparison with Comparative Example 4 reveals that the thin film of Example 31 can be used as a liquid crystal alignment film by subjecting it to irradiation with polarized ultraviolet light and heat treatment at 200° C. or lower.

Claims (14)

Having a structural unit A represented by the following formula (1), 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) A resin composition containing 80 to 99.99% by weight of a polymer having a molecular weight of 0.01 to 20% by weight of a thermal reorientation accelerator having a molecular weight of 200 to 10,000.

(In Formula (1), X ₁ to X ₃ are each independently an optionally substituted C 5 to 7 aromatic ring or an optionally substituted C 5 to 7 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. ₁ to X ₃ each independently represents one 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 X ₁ to X ₃ are substituents is a hydrogen atom, Y ₁ and Y ₂ each independently represent one member of the group consisting of —O—, —CO—, and —NR ₉ —, where R ₉ is hydrogen represents one member of the group consisting of an atom or an alkyl group having 1 to 5 carbon atoms, Ar ₁ and Ar ₂ each independently represent an optionally substituted aromatic ring having 5 to 7 carbon atoms, Any carbon atom in the aromatic ring may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom, wherein the substituents in Ar ₁ and Ar ₂ are each independently a halogen atom, a C 1-5 represents one member of the group consisting of an alkyl group and an alkoxy group having 1 to 5 carbon atoms, and represents a hydrogen atom when Ar ₁ and Ar ₂ do not have a substituent;
R ₁ to 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 a single bond or one of the group consisting of -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 a single bond or one member of the group consisting of -O-, -CO-O-, -CO-NR ₆ -, -CO- and -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 represent 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; )

(In formula (2), Y ₃ and Y ₄ each independently represent one member of the group consisting of —O—, —CO—, and —NR ₁₀ —, where R ₁₀ is a hydrogen atom or the number of carbon atoms represents one member of the group consisting of alkyl groups of 1 to 5. X ₄ to X ₆ each independently have an optionally substituted aromatic ring having 5 to 7 carbon atoms or a substituent; any carbon atom in the aromatic ring or in the alicyclic hydrocarbon group is substituted with a nitrogen atom, an oxygen atom, or a sulfur atom R ₁₁ and R ₁₂ each represent one member of the group consisting of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c represents 0 or 1.)

(In formula (3), Y ₅ and Y ₆ each independently represent one member of the group consisting of —O—, —CO— and —NR ₁₃ —, where R ₁₃ is a hydrogen atom or a carbon number represents one of the group consisting of alkyl groups of 1 to 5. Z is an alicyclic hydrocarbon group of 5 to 7 carbon atoms, a linear alkylene group of 2 to 20 carbon atoms, It represents one of the group consisting of branched alkylene groups.) 2. The resin composition according to claim 1, wherein the polymer has a structural unit A represented by formula (1) and a structural unit B represented by formula (2). 3. The resin composition according to claim 1, wherein Y ₁ and Y ₂ in formula (1) are —O—. 4. The resin composition according to any one of claims 1 to 3, wherein Ar ₁ and Ar ₂ in formula (1) are optionally substituted benzene rings. The resin composition according to any one of claims 1 to 4, wherein the thermal reorientation accelerator is a plasticizer. 5. The resin composition according to any one of claims 1 to 4, wherein the thermal reorientation accelerator is an antioxidant. The resin composition according to any one of claims 1 to 4, wherein the thermal reorientation accelerator is a light stabilizer. An optical thin film comprising the resin composition according to any one of claims 1 to 7. An optical thin film obtained by irradiating the optical thin film according to claim 8 with ultraviolet rays. An optical thin film obtained by irradiating the optical thin film according to claim 9 with polarized ultraviolet rays or oblique incident ultraviolet rays. 11. The optical thin film according to claim 9, wherein the photoreactivity of the photoreactive groups is 50% or less. 12. An optical thin film obtained by heating the optical thin film according to any one of claims 8 to 11 at a temperature within a range in which the resin composition exhibits liquid crystallinity. A retardation film comprising the thin film according to any one of claims 8 to 12. A liquid crystal alignment film comprising the thin film according to any one of claims 8 to 12.