TW201908378A - Layered product, liquid crystal aligning agent, and liquid crystal display element - Google Patents

Abstract

This layered product has: a support; a liquid crystal alignment film that is formed on the support; and an optical anisotropic film that is a transfer film which has an optical compensation function and which is formed on the liquid crystal alignment film. The liquid crystal alignment film is formed by using a liquid crystal aligning agent containing a polymer [A] which has an optical alignment group and which is at least one selected from the group consisting of polyorganosiloxanes, styrene-maleimide copolymers, (meth)acrylic polymers, and polyamic acids (in the case of polyamic acids, the optical alignment group is in the main chain).

Description

Laminated body, liquid crystal alignment agent and liquid crystal display element

[Reciprocal Reference of Related Application] This application is based on Japanese Patent Application No. 2017-140382, filed on Jul. 19, 2011, the content of which is hereby incorporated herein.

The present disclosure relates to a laminate, a liquid crystal alignment agent, and a liquid crystal display element. More specifically, it relates to transferring a transfer film having an optical compensation function to an adherend to impart an optical compensation function to the adhered body. Physical technology.

Various optical materials are used in liquid crystal display devices such as liquid crystal displays. As the optical material, for example, an optical compensation film such as a retardation film, a viewing angle compensation film, or an antireflection film is known. Among these, for example, the retardation film is used for the purpose of eliminating the coloration of the display or eliminating the dependency of the viewing angle due to the change in the display color and contrast due to the visual direction. As the retardation film, a plastic film is stretched or a liquid crystal coating technique is used.

In order to further improve the display quality of a liquid crystal display or the like, various retardation films have been proposed (for example, refer to Patent Document 1 or Patent Document 2). Patent Document 1 and Patent Document 2 disclose that only an optically anisotropic film formed on a liquid crystal alignment film and an optically anisotropic film formed on a plastic film is transferred onto a substrate or a polarizing plate of a liquid crystal display device. The transfer film is attached to impart a desired function to the adherend. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5363022 [Patent Document 2] International Publication No. 2016/158298

[Problems to be Solved by the Invention] When an optical compensation function is applied to an adherend by a transfer film, if the transfer film is difficult to be peeled off from the liquid crystal alignment film, there is a concern that the transfer is performed. After the film is transferred onto the adherend, the liquid crystal alignment film is locally attached to the transfer film. In this case, there is a concern that a sufficient optical compensation function cannot be imparted to the adherend. Further, in the case of use for a display device, in order to sufficiently obtain an optical compensation effect of the transfer film in the adherend, the transfer film is required to be easily peeled off from the liquid crystal alignment film, and the transfer film after transfer The haze value is low and the transmittance is high.

One of the objects of the present disclosure is to provide a liquid crystal alignment agent which is excellent in peelability between a transfer film for forming an optical compensation function and a liquid crystal alignment film, and which has low haze value and high transmittance. A liquid crystal alignment film of the transfer film.

[Means for Solving the Problem] In order to solve the above problems, the present disclosure adopts the following method. <1> A laminate having a support, a liquid crystal alignment film formed on the support, and a transfer film having an optical compensation function formed on the liquid crystal alignment film, and the laminate The liquid crystal alignment film is formed using a liquid crystal alignment agent containing a polyorganosiloxane, a styrene-maleimide copolymer, a (meth)acrylic polymer, and a poly A polymer [A] having at least one of the group consisting of proline and having a photo-alignment group (wherein, in the case of poly-proline, a photo-alignment group in the main chain). <2> A liquid crystal alignment agent for producing a transfer film having an optical compensation function, wherein the liquid crystal alignment agent contains a copolymer selected from the group consisting of polyorganosiloxanes, styrene-maleimide copolymers a polymer [A] having at least one of a group consisting of a (meth)acrylic polymer and a polyamic acid and having a photo-alignment group (wherein, in the case of poly-proline, There is a photo-alignment group in the chain).

<3> A liquid crystal alignment film which is a liquid crystal alignment film provided in a laminate, wherein the laminate has a support, a liquid crystal alignment film formed on the support, and an optical film formed on the liquid crystal alignment film A transfer film that compensates for the function, and the liquid crystal alignment film is formed using the liquid crystal alignment agent as described in <2>. <4> A method for producing a laminate, wherein the laminate has a support, a liquid crystal alignment film formed on the support, and a transfer film having an optical compensation function formed on the liquid crystal alignment film, and The method for producing a laminate includes a step of applying a liquid crystal alignment agent as described in <2> to the support to form a coating film, and irradiating the coating film with light to impart a liquid crystal alignment ability. a step of forming a liquid crystal alignment film on the support; and a step of forming the optically anisotropic film on the liquid crystal alignment film. <5> A method of forming an optical compensation film, which is a method of forming an optical compensation film on an adherend, and a method of forming the optical compensation film, comprising: a transfer of the laminate as described in <1> The step of transferring the printing film onto the adherend.

<6> A method for producing a polarizing film with a retardation film, wherein the method for producing a polarizing film with a retardation film comprises: transferring a transfer film having a laminate as described in <1> a step on the polarizing film. <7> A polarizing film having a retardation film, which is obtained by transferring a transfer film of a laminate according to <1> to a polarizing film. <8> A method of manufacturing a liquid crystal display element, comprising: a step of constructing a liquid crystal cell having a pair of substrates disposed opposite to each other and disposed between the pair of substrates And a step of transferring the transfer film of the laminate according to <1> to the outside of at least one of the pair of substrates of the liquid crystal cell.

[Effects of the Invention] According to the laminated body of the present invention, an optical compensation film having a good liquid crystal alignment property and a high transmittance can be formed on a substrate. Therefore, the liquid crystal display element of the optical compensation film formed on the adherend using the laminated body of the present invention has a high effect of improving the display quality, and thus can be preferably used in the field of image display and the like. Further, according to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having a good transfer property with a transfer film having an optical compensation function and having a low haze value and a high transmittance can be obtained.

Hereinafter, the liquid crystal alignment agent of the present disclosure will be described with reference to the drawings. The liquid crystal alignment agent of the present invention is used for transferring an optically anisotropic film 13 to a support by laminating the laminated body 10 having the support 11, the liquid crystal alignment film 12, and the optically anisotropic film 13 in this order. 11 different substrates (adhered bodies 21) are formed, thereby forming a liquid crystal alignment film 12 for obtaining the adherends 21 having the optically anisotropic film 13. The optically anisotropic film 13 corresponds to a "transfer film". Hereinafter, the components to be formulated in the liquid crystal alignment agent of the present invention and other components which are optionally blended as needed will be described.

<Polymer (A)> The liquid crystal alignment agent of the present invention contains a polymer selected from the group consisting of polyorganosiloxane, styrene-maleimide copolymer, (meth)acrylic polymer, and polyglycolic acid. At least one of the group consisting of the polymer [A] having a photo-alignment group (wherein, in the case of poly-proline, a photo-alignment group in the main chain).

The photo-alignment group of the polymer [A] is a photoisomerization reaction, a photodimerization reaction, a photodecomposition reaction, a photo Fries rearrangement reaction, or the like by light irradiation. An anisotropic functional group is imparted. Specific examples of the photo-alignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, and a cinnamic acid-containing group containing cinnamic acid or a derivative thereof as a basic skeleton. a benzophenone-containing group containing chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, containing coumarin or a derivative thereof as a basic The coumarin-containing group of the skeleton. Among these, the photo-alignment group which the polymer [A] has is preferably one selected from the group consisting of a group containing an azobenzene group and a group containing a cinnamic acid structure. In particular, a group having a cinnamic acid structure is preferred from the viewpoint of having a high alignment ability and being easily incorporated into a polymer. Specifically, a group represented by the following formula (1) is preferred. [Chemical 1] (In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a cyano group; and R ³ is a halogen atom; An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a cyano group; a is an integer of 0 to 4; and when a is 2 or more, a plurality of R ³ may be the same or may be the same Different; X ¹ is an oxygen atom, a sulfur atom or -NR ⁸ - (wherein R ⁸ is a hydrogen atom or a monovalent organic group); "*" means a bond bond)

The group represented by the formula (1) is a monovalent group obtained by removing one hydrogen atom of an amino group carbonyl group of a cinnamic acid or a carboxylic acid decylamine, or a monovalent group. a group in which a substituent is introduced into a benzene ring (hereinafter, referred to as "cis cinnamate group"), or a carboxyl group of cinnamic acid or an aminocarbonyl group of decyl cinnamate a monovalent group which is esterified and bonded to a divalent organic group on a benzene ring or a group in which a substituent is introduced on a benzene ring of the monovalent group (hereinafter, these are also referred to as "reverses" Citrate group") and the like. When X ¹ is -NR ⁸ -, R ^{8 is} preferably a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms or a third butoxycarbonyl group. a is preferably 0 or 1. The cis cinnamate group can be represented, for example, by the following formula (cn-1), and the trans cinnamate group can be represented, for example, by the following formula (cn-2). [Chemical 2] (In the formula (cn-1), R ⁴ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a cyano group; and R ⁵ is a phenyl group and a biphenyl group. a group, a triphenyl or a cyclohexylene group, or at least a part of hydrogen atoms of the groups having a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or the alkoxy group a group or a cyano group in which at least a part of a hydrogen atom of a group is substituted with a monovalent group substituted with a halogen atom; A ¹ is a single bond, an oxygen atom, a sulfur atom, an alkanediyl group having 1 to 3 carbon atoms, -CH=CH -, -NH-, * ¹ -COO-, * ¹ -OCO-, * ¹ -NH-CO-, * ¹ -CO-NH-, * ¹ -CH ₂ -O- or * ¹ -O-CH ₂ -("* ¹ " represents a bond with R ⁵ ); b is 0 or 1; in the formula (cn-2), R ⁶ is an alkyl group having 1 to 3 carbon atoms; A ² is an oxygen atom, * ² -COO-, * ² -OCO-, * ² -NH-CO- or * ² -CO-NH- ("* ² " represents a bond to R ⁷ ); R ⁷ is an alkane having 1 to 6 carbon atoms a dibasic group; c is 0 or 1; and R ¹ , R ² , R ³ , X ¹ and a in the formula (cn-1) and the formula (cn-2) have the same meanings as in the formula (1); ” indicates the key button)

In the polymer [A], the content ratio of the photo-alignment group is preferably from 1 mol% to 70 mol%, more preferably from the total amount of the monomer used in the synthesis of the polymer [A]. 3 mol% to 60 mol%, and more preferably 5 mol% to 60 mol%.

The liquid crystal alignment agent of the present disclosure is preferably the same molecule as the polymer [A] from the viewpoint of obtaining a liquid crystal alignment film which is more excellent in peelability, transparency, and liquid crystal alignment property with an optically anisotropic film. A polymerizable group is contained in the molecule or in a different molecule from the polymer [A]. In particular, when the polymer [A] further has a polymerizable group, the effect of improving the peeling property, transparency, and liquid crystal alignment of the optically anisotropic film with respect to the liquid crystal alignment film is high. In addition, the reason why the effect is further increased when the component in the liquid crystal alignment agent has a polymerizable group is presumed to be the intermolecular or intramolecular crosslinking caused by the polymerizable group, and the hardness of the liquid crystal alignment film is changed. When the adhesion of the liquid crystal alignment film to the support is improved, the optically anisotropic film is perfectly peeled off from the liquid crystal alignment film, and as a result, the alignment regulating force and transparency of the optically anisotropic film become high.

The polymerizable group is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat, and examples thereof include (meth)acryl fluorenyl group, vinyl group, vinyl phenyl group, and sub Vinyl, vinyloxy (CH ₂ =CH-O-), maleimide, allyl, ethynyl, allyl, allyloxy, cyclic ether (oxyheterocycle) Butyl, oxiranyl, etc.) and the like. Among these, a (meth) acrylonitrile group and an epoxy group are preferable in terms of high reactivity with respect to light. Further, the (meth)acrylonitrile group has the meaning of an acryloyl group and a methacryl group, and the epoxy group has the meaning of an oxacyclopropyl group and an oxetanyl group. The content ratio of the polymerizable group is preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, based on the entire monolithic unit constituting the polymer [A].

The polymer [A] can be obtained by a synthesis method corresponding to the main skeleton. Hereinafter, polyorganosiloxane, styrene-maleimide copolymer, (meth)acrylic polymer, and polyglycolic acid will be described.

(Polyorganosiloxane) The method of synthesizing a polyorganosiloxane having a photo-alignment group (hereinafter also referred to as "polyorganosiloxane [A]") is not particularly limited, and it is simple and can improve optical alignment. In terms of the introduction rate of a group, it is preferably obtained by hydrolyzing and condensing a mixture of an epoxy group-containing alkoxydecane or an epoxy group-containing alkoxysilane with another decane compound. The epoxy group-containing polyorganosiloxane is then reacted with the obtained epoxy group-containing polyorganosiloxane and a photo-alignment group-containing carboxylic acid (hereinafter also referred to as "specific carboxylic acid").

The epoxy group-containing polyorganosiloxane can be obtained, for example, by hydrolysis/condensation of a hydrolyzable decane compound. The decane compound to be used is not particularly limited as long as it exhibits hydrolyzability, and examples thereof include tetraalkoxydecane, phenyltrialkoxydecane, dialkyldialkoxydecane, and monoalkyltrioxane. Oxydecane, mercaptoalkyltrialkoxydecane, ureidoalkyltrialkoxydecane, aminoalkyltrialkoxydecane, 3-glycidoxypropyltrialkoxydecane, 2-( 3,4-epoxycyclohexyl)ethyltrialkoxydecane, 3-(3,4-epoxycyclohexyl)propyltrialkoxydecane, 3-(methyl)propenyloxypropyl three Alkoxydecane, vinyltrialkoxydecane, p-styryltrialkoxydecane, trimethoxydecylpropylsuccinic anhydride, and the like. The decane compound may be used alone or in combination of two or more.

The hydrolysis of the decane compound × condensation reaction is carried out by reacting one or two or more kinds of the above-described decane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. When the hydrolysis x condensation reaction is carried out, the use ratio of water is preferably from 1 mole to 30 moles per mole of the decane compound (total amount). Examples of the catalyst include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. The amount of the catalyst to be used varies depending on the type of the catalyst, the reaction conditions, and the like, and is appropriately set. For example, the total amount of the catalyst is preferably 0.05 to 1 mol per mol of the total amount of the decane compound. Examples of the organic solvent used in the reaction include a hydrocarbon, a ketone, an ester, an ether, and an alcohol. Among these, it is preferred to use an organic solvent which is not water-soluble or poorly water-soluble. The use ratio of the organic solvent is preferably from 10 parts by mass to 1,000 parts by mass based on 100 parts by mass of the total of the decane compound used in the reaction.

The hydrolysis × condensation reaction is preferably carried out, for example, by heating (for example, heating to 40 ° C to 130 ° C) by an oil bath or the like. The heating time is preferably set to 0.5 hours to 8 hours. After completion of the reaction, the organic solvent layer separated from the reaction liquid is washed with water as needed, and the organic solvent layer is dried with a desiccant to remove the solvent, whereby the target polyorganosiloxane can be obtained. Further, the method for synthesizing the polyorganosiloxane is not limited to the hydrolysis × condensation reaction, and may be carried out, for example, by a method in which a hydrolyzable decane compound is reacted in the presence of oxalic acid and an alcohol.

Then, the obtained epoxy group-containing polyorganosiloxane is reacted with a specific carboxylic acid. Thereby, the epoxy group of the epoxy group-containing polyorganosiloxane is reacted with a carboxylic acid to obtain a polyorganosiloxane [A].

The specific carboxylic acid is not particularly limited as long as it has a photo-alignment group, and is preferably a carboxylic acid having a group having a cinnamic acid structure. As such a specific carboxylic acid, for example, a part of a bond bond in a group in which X ¹ of the formula (cn-1) and the formula (cn-2) is an oxygen atom is bonded A carboxylic acid of a hydrogen atom or the like. Further, the specific carboxylic acids may be used alone or in combination of two or more.

When the epoxy group-containing polyorganosiloxane is reacted with a specific carboxylic acid, a carboxylic acid (other carboxylic acid) having no photo-alignment group can also be used. The other carboxylic acid to be used is not particularly limited, and a carboxylic acid having a polymerizable group (hereinafter also referred to as "polymerizable group-containing carboxylic acid") can be preferably used, and the polymerizable group can be more preferably used. A (meth)acrylonitrile-based carboxylic acid. When the epoxy group-containing polyorganosiloxane is reacted with a specific carboxylic acid, a liquid crystal alignment film having better peelability between the optically anisotropic film and the liquid crystal alignment film can be obtained by using the polymerizable group-containing carboxylic acid in combination. It is better in this respect. As a specific example of the polymerizable group, the description relating to the polymerizable group which the polymer [A] can have can be applied. The polyorganosiloxane [A] preferably has at least an epoxy group, more preferably a (meth) acryloyl group and an epoxy group. The carboxylic acid which is reacted with the epoxy group-containing polyorganosiloxane is also a carboxylic acid anhydride.

Specific examples of the polymerizable group-containing carboxylic acid include (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and w-carboxyl-poly An unsaturated carboxylic acid such as lactone mono(meth)acrylate or monohydroxyethyl (meth) acrylate; trimellitic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, cis An unsaturated polycarboxylic acid anhydride such as formula-1, 2,3,4-tetrahydrophthalic anhydride or the like. The carboxylic acid having a polymerizable group may be used alone or in combination of two or more kinds. As the other carboxylic acid, in addition to the carboxylic acid having a polymerizable group, for example, propionic acid, benzoic acid, methylbenzoic acid, a carboxylic acid having a vertical alignment group, or the like can be used.

In the case of reacting an epoxy group-containing polyorganosiloxane with a carboxylic acid, the epoxy is possessed with respect to the polyorganosiloxane from the viewpoint of sufficiently proceeding the reaction and reducing the amount of the unreacted carboxylic acid. In view of the fact that the ratio of the carboxylic acid is preferably from 0.001 mol to 1.5 mol, and the liquid crystal alignment film having better peelability between the optically anisotropic film and the liquid crystal alignment film is obtained, More preferably, it is set to 0.01 mol or more and less than 1.0 mol, and more preferably 0.1 mol to 0.8 mol. When the reaction is carried out, the photo-alignment group can be obtained by setting the ratio of the carboxylic acid to less than 1 mol with respect to 1 mol of the epoxy group of the polyorganosiloxane. The epoxy group polyorganosiloxane [A] is preferred in this respect. The polyorganosiloxane [A] preferably has an epoxy group in a side chain in terms of further improving the releasability of the liquid crystal alignment film and the optically anisotropic film.

From the viewpoint of improving the liquid crystal alignment property of the liquid crystal alignment film 12, the ratio of use of the specific carboxylic acid (total amount when two or more types are used) is compared with the total amount of the carboxylic acid used in the reaction. Preferably, it is set to 10 mol% or more, and more preferably 20 mol% or more. When a carboxylic acid containing a polymerizable group is used, the use ratio of the polymerizable group-containing carboxylic acid is preferably 1 mol% or more, more preferably 1 part or more, based on the total amount of the carboxylic acid used in the reaction. It is set to 3 mol% to 50 mol%, and more preferably 5 mol% to 30 mol%.

The reaction of the epoxy group-containing polyorganosiloxane with the carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst, a tertiary organic amine or a tertiary organic amine is preferably used. The use ratio of the catalyst is preferably from 0.1 part by mass to 20 parts by mass based on 100 parts by mass of the epoxy group-containing polyorganosiloxane. The organic solvent to be used is preferably at least one selected from the group consisting of ethers, esters, and ketones from the viewpoint of solubility of the raw materials and products and easiness of purification of the product. Specific examples of the particularly preferable solvent include 2-butanone, 2-hexanone, methyl isobutyl ketone, and butyl acetate. The organic solvent is preferably used in a ratio of a solid content concentration (a ratio of a total mass of components other than the solvent in the reaction solution to the total mass of the solution) of 5% by mass to 50% by mass. The reaction temperature is preferably from 0 ° C to 200 ° C, and the reaction time is preferably from 0.1 to 50 hours. After completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid by using water.

The polyorganosiloxane [A] preferably has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in a range of from 100 to 50,000. More preferably, it is in the range of 200 to 10,000.

(Styrene-maleimide copolymer) The styrene-maleimide copolymer (hereinafter also referred to as "polymer [As]") as the polymer [A] has The photo-alignment group preferably further has a polymerizable group. The polymerizable group of the polymer [As] is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat, and examples thereof include (meth)acryl fluorenyl group and vinyl group. A vinyl phenyl group, a vinyl ether group, an allyl group, an ethynyl group, an allyl group, an allyloxy group, a cyclic ether group, a group represented by the following formulas (22) to (25), and the like. In the following formula, examples of the divalent organic group of R ¹² to R ¹⁵ include a divalent hydrocarbon group having 1 to 20 carbon atoms and a -O-, - between the carbon-carbon bonds of the divalent hydrocarbon group. A base such as CO-, -COO-, or the like. Among these, the polymerizable group of the polymer [As] is preferably a (meth) acrylonitrile group or an epoxy group, and more preferably an epoxy group. [Chemical 3] (In the formulae (22) to (25), R ¹² to R ¹⁴ are each independently a single bond or a divalent organic group, and R ¹⁵ is a divalent organic group; "*" represents a bond bond)

The polymer [As] may contain only a structural unit derived from a monomer having a styryl group (hereinafter, also referred to as "styrene compound") and a monomer derived from a maleimide group. The structural unit (hereinafter also referred to as "methyleneimine-based compound") may further contain a structural unit derived from a singly-based compound other than a styrene-based compound or a maleimide-based compound. . The content ratio of the structural unit derived from the styrene-based compound is preferably from 2 mol% to 80 mol%, more preferably 5 mol, based on all the structural units of the styrene-maleimide copolymer. Ear % ~ 70 mol%. Further, the content of the structural unit derived from the maleimide-based compound is preferably from 2 mol% to 80 mol% based on all the structural units of the styrene-maleimide-based copolymer. %, more preferably 5 mol% to 70 mol%.

Specific examples of the styrene-based compound include styrene, methylstyrene, divinylbenzene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, and 3-(glycidoxymethyl). Styrene, 4-(glycidoxymethyl)styrene, 4-glycidyl-α-methylstyrene, and the like. Examples of the maleimide-based compound include N-methyl maleimide, N-cyclohexyl maleimide, and N-phenyl maleimide. , 3-(2,5-dioxo-3-pyrroline-1-yl)benzoic acid, 4-(2,5-dioxo-3-pyrroline-1-yl)benzoic acid, 4-( Methyl 2,5-dioxo-3-pyrroline-1-yl)benzoate, a photo-alignment group-containing compound represented by the following formula (m3-1) to formula (m3-5), and the like. [Chemical 4] Further, as the styrene-based compound or the maleimide-based compound, one type of these may be used alone or two or more types may be used in combination.

The polymer [As] can be obtained by polymerization using a styrene-based compound and a maleimide-based compound. The polymerization is preferably carried out in the presence of a polymerization initiator and in an organic solvent. As the polymerization initiator to be used, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2 are preferable. An azo compound such as '-azobis(4-methoxy-2,4-dimethylvaleronitrile). The use ratio of the polymerization initiator is preferably from 0.01 part by mass to 30 parts by mass based on 100 parts by mass of all the monomers used in the reaction. Examples of the organic solvent to be used include an alcohol, an ether, a ketone, a decylamine, an ester, and a hydrocarbon compound. In this case, the reaction temperature is preferably from 30 ° C to 120 ° C, and the reaction time is preferably from 1 hour to 36 hours. The amount (a) of the organic solvent used is preferably an amount of from 0.1% by mass to 60% by mass based on the total amount (b) of the monomers used in the reaction with respect to the total amount (a+b) of the reaction solution.

In terms of further improving the releasability of the liquid crystal alignment film and the optically anisotropic film, the polymer [As] is preferably an epoxy group, a functional group reactive with an epoxy group by heating, and a photoalignment property. A styrene-maleimide copolymer. The functional group which reacts with the epoxy group by heating is preferably a carboxyl group or a protective carboxyl group from the viewpoint of high storage stability and high reactivity with an epoxy group. In the case where the polymer [As] has an epoxy group and a functional group reactive with an epoxy group by heating, the polymer is [the total amount of the unitary body used in the synthesis of the polymer [As] [ The content of the epoxy group in As] is preferably from 1 mol% to 60 mol%, more preferably from 10 mol% to 50 mol%. Further, the content ratio of the functional group reactive with the epoxy group by heating is preferably from 1 mol% to 90 mol%, more preferably from 10 mol% to 80 mol%.

The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 1,000 to 300,000, and more preferably 2,000 to 100,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 10 or less, more preferably 8 or less.

((meth)acrylic polymer) The (meth)acrylic polymer (hereinafter also referred to as "polymer [Am]") as the polymer [A] has a photo-alignment group, and preferably further has Polymeric group. The polymer [Am] preferably has an epoxy group as a polymerizable group in the side chain. Such a polymer [Am] can be obtained, for example, by polymerizing a monomer having a (meth)acrylic compound having an epoxy group in the presence of a polymerization initiator, and then obtaining the obtained The polymer (hereinafter also referred to as "epoxy group-containing poly(meth)acrylate") is reacted with a photo-alignment group-containing carboxylic acid and a polymerizable group-containing carboxylic acid. Further, the description of the polymer [As] can be applied to various conditions in the synthesis reaction.

Examples of the epoxy group-containing (meth)acrylic monomer are, for example, an unsaturated carboxylic acid ester having an epoxy group. Specific examples thereof include glycidyl (meth)acrylate and α-. Glycidyl ethacrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate And 4-hydroxybutyl glycidyl ether acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, and the like.

In the case of carrying out the polymerization, a monovalent body other than the epoxy group-containing (meth)acrylic monomer may be used in combination with an epoxy group-containing (meth)acrylic monomer. Acrylic acid, maleic acid, vinyl benzoic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, (a) Cyclohexyl acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzene Ethylene, methyl styrene, N-methyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, and the like. Further, the other singly-sized ones may be used alone or in combination of two or more.

The number average molecular weight (Mn) in terms of polystyrene measured by GPC in the polymer [Am] is preferably from 250 to 500,000, more preferably from 500 to 100,000, still more preferably from 1,000 to 50,000.

(Polyamic acid) The polylysine as the polymer [A] has a photo-alignment group in the main chain. The polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine compound. In terms of high selectivity of the monomer, it is preferably obtained by polymerization of a diamine (hereinafter, also referred to as "specific diamine") containing a photoreactive group in the main chain. The tetracarboxylic dianhydride used in the synthesis of the poly-proline is not particularly limited, and various conventionally known tetracarboxylic acids such as tetracarboxylic dianhydride described in JP-A-2010-97188 can be used. Diacid anhydride. As the specific diamine, an aromatic diamine represented by the following formula (2) can be preferably used. [Chemical 5] (In the formula (2), X ² and X ³ are each independently a single bond or a divalent linking group, and Y ¹ is a divalent group represented by the formula (1); a is 0 or 1; wherein, a In the case of 0, X ² is a single bond, and the amine group in the formula (2) is bonded to the benzene ring in the formula (1))

Specific examples of the specific diamine include a compound represented by the following formula and the like. Further, the specific diamine may be used alone or in combination of two or more. [Chemical 6]

In the synthesis of polyamic acid, other diamines other than the specific diamine may be used in combination. The other diamine compound, such as a diamine described in JP-A-2010-97188, can be used. When the other diamine is used in combination, the specific diamine is preferably used in an amount of 10 mol% or more, more preferably 30 mol% or more, based on the total amount of the diamine compound used in the synthesis. .

The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably from -20 ° C to 150 ° C, and the reaction time is preferably from 0.1 hour to 24 hours. Examples of the organic solvent used in the reaction include an aprotic polar solvent, a phenol-based solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. The amount of the organic solvent to be used is preferably from 0.1% by mass to 50% by mass based on the total amount of the tetracarboxylic dianhydride and the diamine compound.

The polystyrene acid has a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC of preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw/Mn) is preferably 7 or less, more preferably 5 or less.

The polymer [A] is preferably selected from the group consisting of polyorganisms in terms of the releasability of the optically anisotropic film and the transparency of the optically anisotropic film after transfer. At least one of a group consisting of a siloxane, a styrene-maleimide copolymer having a polymerizable group, and a (meth)acrylic polymer having a polymerizable group and having optical alignment The polymer of the group is more preferably a polyorganosiloxane having a photo-alignment group. By using a polyorganosiloxane having a photo-alignment group as at least a part of a polymer component in the liquid crystal alignment agent of the present invention, the effect of reducing the surface roughness of the liquid crystal alignment film is high, and the liquid crystal alignment can be achieved. The film and the optically anisotropic film are more excellent in peelability, and are preferable in this respect. Further, since the heating temperature at the time of film formation can be set to a relatively low temperature (for example, 150 ° C or lower), it is also preferable from the viewpoint of the limitation of the substrate which can be used and the energy reduction. The content ratio of the polymer [A] is preferably 5 parts by mass or more, and more preferably 5 parts by mass to 90 parts by mass, based on 100 parts by mass of the total of the polymer components contained in the liquid crystal alignment agent. More preferably, it is 10 mass parts - 80 mass parts. In addition, as one of the reasons, it is presumed that the main skeleton of the polymer [A] is one of the above, and the adhesion of the liquid crystal alignment film to the optically anisotropic film is moderately weak, whereby the optical can be made optical. The anisotropic film has good peelability.

<Other Components> The liquid crystal alignment agent of the present invention may contain other components than the polymer [A] as needed. Examples of the other component include a polymer different from the polymer [A] (hereinafter also referred to as "other polymer"), a curing catalyst, a curing accelerator, and the like.

(Other Polymers) The liquid crystal alignment agent of the present invention preferably contains the polymer [A] and other polymers in order to further improve the electrical properties and liquid crystal alignment properties of the liquid crystal alignment film. The other polymer is not particularly limited, and examples thereof include polyacrylic acid, polyglycolate, polyimide, polyester, polyamine, cellulose derivative, polyacetal, and polystyrene. A polymer having a main skeleton such as a styrene-maleimide copolymer or a (meth)acrylic polymer and different from the polymer [A]. The other polymer preferably has no photo-alignment group, and more preferably has a main chain selected from the group consisting of polyglycine, polyphthalate, polyamidiene and (meth)acrylic polymers. Any of the groups. When the other polymer is blended, the use ratio of the other polymer is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less based on 100 parts by mass of the total of the polymer [A] and the other polymer.

(Curing Catalyst) The curing catalyst is a component having a catalytic action against a crosslinking reaction between the epoxy structures, and is contained in the liquid crystal alignment agent for the purpose of promoting the crosslinking reaction. The hardening catalyst is preferably a metal chelate compound, preferably an acetonitrile acetone complex or an acetoacetate complex using a metal selected from the group consisting of aluminum, titanium and zirconium. Specific examples thereof include aluminum diisopropoxyethylacetate acetate, aluminum tris(acetylacetonate), aluminum tris(ethylacetate acetate), and diisopropoxy bis ( Ethylacetamidine acetate) titanium, diisopropoxy bis(acetyl acetonate) titanium, tri-n-butoxyethyl acetonitrile acetate zirconium, di-n-butoxy bis (ethyl ethyl Indole acetate) zirconium and the like. The use ratio of the metal chelate compound is preferably from 0.1 part by mass to 50 parts by mass, more preferably from 0.5 part by mass to 30 parts by mass, per 100 parts by mass of the total of the polymer component in the liquid crystal alignment agent.

(Curing Agent) The curing accelerator is a component contained in the liquid crystal alignment agent for the purpose of enhancing the catalytic action of the curing catalyst and promoting the crosslinking reaction between the epoxy structures. As the hardening accelerator, for example, a compound having a phenol group, a stanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group or the like can be used. Specific examples of the effect accelerator include cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol, trimethylstanol, and triethyl. Hydranol, 1,1,3,3-tetraphenyl-1,3-dioxanediol, 1,4-bis(hydroxydimethylalkylalkyl)benzene, triphenylstanol, three (pair) Tolyl) decyl alcohol, diphenyl decane diol, trimellitic acid, and the like. The use ratio of the curing accelerator is preferably 30 parts by mass or less, more preferably 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of the total of the polymer components in the liquid crystal alignment agent.

Further, the liquid crystal alignment agent may contain components other than the above without departing from the objects and effects of the present disclosure. Examples of the component include a compound having at least one epoxy group in the molecule, a functional decane compound, a surfactant, cerium oxide particles, a filler, an antifoaming agent, a photosensitizer, a dispersing agent, and the like. Antioxidant, adhesion aid, antistatic agent, antibacterial agent, ultraviolet absorber, etc. Further, the blending ratios of these may be appropriately set within the range not impairing the effects of the present disclosure depending on the respective compounds to be formulated.

(Solvent) The liquid crystal alignment agent is prepared in the form of a liquid composition in which the polymer [A] and any other components used are preferably dispersed or dissolved in a suitable solvent. The solvent to be used is preferably an organic solvent, and an alcohol, an ether, a ketone, a guanamine, an ester, a hydrocarbon or the like can be preferably used. Among them, it is preferred to use one or more solvents selected from the group consisting of partial esters, polyol ethers, ethers, ketones and esters of polyhydric alcohols (hereinafter also referred to as "A solvent"). Specifically, as a partial ester of a polyhydric alcohol, propylene glycol monomethyl ether acetate can be preferably used; as the polyol ether, a propylene glycol monomethyl ether and ethylene glycol monobutyl ether (butyl soluble fiber) can be preferably used. One or more of the agents; as the ether, one or more selected from the group consisting of diethylene glycol ethyl methyl ether and tetrahydrofuran; and as the ketone, a methyl ethyl ketone or a ring selected from the group consisting preferably More than one of pentanone and cyclohexanone; as the ester, it is preferably selected from the group consisting of ethyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, ethyl acetate and propylene glycol monomethyl More than one of ether acetates.

In the preparation of the liquid crystal alignment agent, the A solvent may be used alone as the solvent, or the A solvent and other solvents (hereinafter also referred to as "B solvent") may be used at the same time. Examples of the B solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and 1,2-dimethyl-2-imidazolidinone. N,N-dimethylformamide and the like. The solvent B may be used alone or in combination of two or more. The ratio of use of the A solvent and the B solvent to be used can be appropriately selected depending on the solubility of the polymer with respect to the solvent. Specifically, in the case where the polymer [A] is at least one selected from the group consisting of a polyorganosiloxane and a (meth)acrylic polymer, the preparation of the liquid crystal alignment agent is The total amount of the solvent to be used is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. In addition, the use ratio of the B solvent is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20%, based on the total amount of the solvent used in the preparation of the liquid crystal alignment agent. Below mass%. In the case where the styrene-maleimide-based copolymer and the poly-proline are contained as the polymer [A], the total amount of the solvent used in the preparation of the liquid crystal alignment agent, the use of the A solvent The ratio is preferably 5% by mass or more, and more preferably 10% by mass or more. In addition, the use ratio of the B solvent is preferably 95% by mass or less, and more preferably 90% by mass or less based on the total amount of the solvent used in the preparation of the liquid crystal alignment agent.

In view of the applicability of the liquid crystal alignment agent and the film thickness of the formed coating film, the use ratio of the solvent is preferably set to be a solid content concentration of the liquid crystal alignment agent (all other than the solvent in the liquid crystal alignment agent). The ratio of the total mass of the components to the total mass of the polymer composition is 0.2% by mass to 10% by mass, and more preferably 3% by mass to 10% by mass.

<Laminated body and method for producing the same> As shown in FIG. 1 , the laminated body 10 of the present invention is formed by sequentially laminating the support 11 , the liquid crystal alignment film 12 , and the optical anisotropic film 13 . The optically anisotropic film 13 is a film containing a liquid crystal compound, and may be a film including a single layer or a film including a plurality of layers. Examples of the case where the optical anisotropic film 13 has a multilayer structure include, for example, a multilayer structure in which two or more liquid crystal layers having different retardations are laminated, and another layer is interposed between the liquid crystal layer and the liquid crystal layer (for example, , a layer or an adhesive layer, etc.). The laminated body 10 can be manufactured, for example, by the method including the following steps 1 to 3.

(Step 1: Formation of Coating Film) First, a liquid crystal alignment agent is applied onto the support 11, and it is preferred to heat the coated surface to form a coating film on the support 11. As the support 11, a transparent resin film can be preferably used. Specific examples include, for example, deuterated cellulose, polyethylene terephthalate, polybutylene terephthalate, polyfluorene, polyether oxime, polyether ether ketone, polyamine, polyphthalamide. A film of a synthetic resin such as an amine, a poly(meth)acrylate, a polymethyl methacrylate, a polycarbonate, or a cyclic polyolefin. As the support 11, among these, triacetyl cellulose, polyethylene terephthalate, poly(meth) acrylate, polycarbonate or polyether ether ketone is preferable. The support 11 is moderately resistant to a solvent (a solvent of only A solvent or a mixed solvent of A solvent and B solvent) which is preferably used in the preparation of the liquid crystal alignment agent containing the polymer [A], and can be formed on the support. The liquid crystal alignment film on the film 11 has better adhesion to the support 11 and liquid crystal alignment, and in this respect, the synthetic resin is preferable. In order to make the surface of the support 11 and the liquid crystal alignment film 12 more excellent in adhesion to the support 11 to be used, a conventionally known pretreatment such as alkalizing treatment may be applied to the surface on which the liquid crystal alignment film 12 is formed.

The coating of the support 11 by the liquid crystal alignment agent can be carried out by a suitable coating method. Specifically, for example, a roll coater method, a spinner method, an inkjet printing method, a bar coater method, an extrusion die method, a direct gravure coater method, or a chamber blade coating method can be employed. Machine method, offset gravure coater method, impregnation coater method, MB coater method, and the like. After the application of the liquid crystal alignment agent, it is preferred to heat (bake) the coated surface. The heating temperature at this time is preferably from 40 ° C to 150 ° C, more preferably from 80 ° C to 140 ° C. The heating time is preferably from 0.1 minute to 15 minutes, more preferably from 1 minute to 10 minutes. The film thickness of the coating film formed on the support 11 is preferably from 1 nm to 1 μm, more preferably from 5 nm to 0.5 μm. Thereby, the coating film which becomes the liquid crystal alignment film 12 is formed in the support body 11.

(Step 2: Light alignment treatment) Then, the coating film formed on the substrate in the manner described above is irradiated with light to impart a liquid crystal alignment ability to the coating film, thereby forming the liquid crystal alignment film 12. Here, examples of the irradiation light include ultraviolet rays, visible rays, and the like including light having a wavelength of 150 nm to 800 nm. Among these, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. The illumination light may be polarized or non-polarized. As the polarized light, it is preferred to use light including linearly polarized light. When the light to be used is polarized, the light may be emitted from a direction perpendicular to the substrate surface, or may be performed from an oblique direction, or may be combined. In the case of irradiating non-polarized light, it is necessary to proceed from a direction inclined with respect to the substrate surface.

Examples of the light source to be used include a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and a mercury-xenon lamp (Hg-Xe lamp). The polarized light can be obtained by a method in which the light sources are used in combination with, for example, a filter, a diffraction grating, or the like. The amount of light to be irradiated is preferably from 0.1 mJ/cm ² to 1,000 mJ/cm ² , more preferably from 1 mJ/cm ² to 500 mJ/cm ² .

(Step 3: Formation of Optically Anisotropic Film) Then, the polymerizable liquid crystal is applied onto the coating film (liquid crystal alignment film 12) which has been subjected to light irradiation as described above, and is cured. Thereby, an optically anisotropic film 13 as a transfer film having an optical compensation function is formed on the surface of the liquid crystal alignment film 12. The polymerizable liquid crystal used herein is a liquid crystal compound polymerized by at least any one of heating and light irradiation. Examples of the polymerizable group of the polymerizable liquid crystal include a (meth)acryl fluorenyl group, a vinyl group, a vinylphenyl group, an allyl group and the like, and a (meth) acrylonitrile group is preferable.

The polymerizable liquid crystal may be any liquid crystal compound having a polymerizable functional group, and those known in the art can be used. Specifically, for example, the nematic liquid crystal described in Non-Patent Document 1 ("UV-curable liquid crystal and its application", liquid crystal, Vol. 3, No. 1 (1999), pp 34 to 42). In this case, a liquid crystal compound having a (meth) acrylonitrile group and a mesogen skeleton is preferred. Further, it may be a cholesteric liquid crystal, a discotic liquid crystal, or a twisted nematic alignment type liquid crystal to which a chiral agent is added. In the case of forming an optically anisotropic film using a polymerizable liquid crystal, a mixture of a plurality of liquid crystal compounds may be used, and a known polymerization initiator, a suitable solvent, a polymerizable monomer, a surfactant, or the like may be further used. Composition. When a polymerizable liquid crystal is applied onto the formed liquid crystal alignment film 12, for example, a suitable coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, or an inkjet method can be employed.

Then, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from the group consisting of heating and light irradiation, whereby the coating film is cured to form a liquid crystal layer (optical anisotropic film 13). In terms of obtaining a good alignment, it is preferred to carry out the treatments in an overlapping manner. The heating temperature of the coating film can be appropriately selected depending on the type of the polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck, it is preferred to carry out heating at a temperature in the range of 40 to 80 °C. The heating time is preferably from 0.5 minutes to 5 minutes. As the irradiation light to the coating film, non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be preferably used. The amount of light to be irradiated is preferably 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably 100 mJ/cm ² to 5,000 mJ/cm ² . In addition, the irradiation of the polarized radiation of the coating film may be performed only once from a predetermined polarization direction, and the coating film may be irradiated with radiation having a plurality of polarization directions (incident directions).

The thickness of the optically anisotropic film 13 to be formed can be appropriately set in accordance with desired optical characteristics. For example, when a 1/2 wavelength plate of visible light having a wavelength of 540 nm is produced as a retardation film, the phase difference of the optically anisotropic film 13 as a retardation film is selected to be a thickness of 240 nm to 300 nm. In the case of a 1/4 wavelength plate, a thickness such as a phase difference of 120 nm to 150 nm is selected. The thickness of the optically anisotropic film 13 at which the target phase difference can be obtained varies depending on the optical characteristics of the polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness for producing a quarter-wave plate is in the range of 0.6 μm to 1.5 μm. In this way, the laminated body 10 is obtained. In the case where the optical anisotropic film 13 has a multilayer structure, the optically anisotropic film 13 can be obtained, for example, by repeatedly applying and hardening a polymerizable liquid crystal.

<Method of Forming Optical Compensation Film> The optically anisotropic film 13 of the laminated body 10 is transferred onto the adherend 21 by the laminated body 10, whereby the optical compensation film 23 can be formed on the adhered body 21. . Specifically, first, the laminated body 10 is obtained as described above (see (a) of FIG. 1 ), and then the surface of the laminated body 10 on the side of the optically anisotropic film 13 is bonded to the surface of the adherend 21 . (Refer to (b) of Fig. 1). In this case, the bonding layer 22 may be formed on at least one of the surface on the optical anisotropic film 13 side of the laminated body 10 and the surface of the adherend 21, and the laminated body 10 and the adherend may be adhered via the bonding layer 22. 21 fits. Then, the support 11 is separated from the adherend 21 . Thereby, peeling occurs at the boundary portion between the liquid crystal alignment film 12 and the optical anisotropic film 13, and the optical anisotropic film 13 is transferred onto the surface of the adherend 21. In this manner, the optical compensation film 23 including the optically anisotropic film 13 is formed on the adherend 21 (see (c) of FIG. 1). Examples of the optical compensation film 23 include a retardation film, a viewing angle compensation film, and an antireflection film.

The adherend 21 of the transfer optical anisotropic film 13 is not particularly limited. For example, a liquid crystal cell in which a liquid crystal layer is provided between a pair of substrates arranged in opposite directions is formed, and a pair of substrates (for example, glass substrates) in the liquid crystal cell is used as the adherend 21 . Then, the surface of the laminated body 10 on the side of the optically anisotropic film 13 is bonded to the outside of at least one of the pair of substrates to transfer the optically anisotropic film 13. Thereby, a liquid crystal display element having an optical compensation film 23 including the optical anisotropic film 13 on the outer side of a pair of substrates in the liquid crystal cell can be obtained. Alternatively, the polarizing film may be the adherend 21, and the surface of the laminated body 10 on the side of the optically anisotropic film 13 may be bonded to the polarizing film (preferably on the surface on the polarizing layer side of the polarizing film). The optical anisotropic film 13 is transferred. When the optically anisotropic film 13 is transferred onto the surface of the polarizing film on the side of the polarizing layer, the transferred surface of the polarizing film is preferably a material having a small shrinkage at the time of transfer, and includes triacetyl cellulose. A protective layer of (Triacetyl Cellulose, TAC) or a liquid crystal layer having iodine adsorbed on polyvinyl alcohol. When the optically anisotropic film 13 is a retardation film, a polarizing film (a polarizing film with a retardation film) having the optically anisotropic film 13 can be obtained. The polarizing film with a retardation film can be used, for example, as a circularly polarizing plate. Further, the transfer film is effectively used as a transfer film having an antireflection function by being combined with a linear polarizing plate. The adherend 21 is preferably a glass substrate, a triacetyl cellulose layer or a polyvinyl alcohol layer, more preferably a glass substrate or a triacetyl cellulose layer.

The plurality of laminated bodies 10 can also be used to transfer the plurality of optically anisotropic films 13 to the adherend 21 . Specifically, first, the first layered body in which the first liquid crystal alignment film and the first optical anisotropic film are sequentially laminated on the support is bonded to one surface of the adherend 21, whereby the first optical body is used. The anisotropic film is transferred onto the adherend 21 . Then, the second layered body in which the second liquid crystal alignment film and the second optical anisotropic film are sequentially laminated on the support is bonded to the formation surface of the first optical anisotropic film in the adherend 21 The second optical anisotropic film is transferred onto the surface of the first optical anisotropic film. Thereby, an optical compensation film including a multilayer optical structure including the first optical anisotropic film and the second optical anisotropic film can be formed on one surface of the adherend 21 . Further, in the optical compensation film including the multilayer structure, the optically anisotropic layer is not limited to two layers, and may be three or more layers.

[Examples]

Hereinafter, the details will be further specifically described by way of examples, but the contents of the present disclosure are not limited to the examples.

In the following examples, the weight average molecular weight Mw, the number average molecular weight Mn and the epoxy equivalent of the polymer, and the solution viscosity of the polymer solution were measured by the following methods. The amount of the raw material compound and the polymer used in the following examples is ensured by repeating the synthesis at the synthesis scale shown in the following synthesis examples as needed.

[The weight average molecular weight Mw and the number average molecular weight Mn of the polymer] Mw and Mn are polystyrene-converted values measured by GPC under the following conditions. Pipe column: manufactured by Tosoh Co., Ltd., TSKgelGRCXLII Solvent: tetrahydrofuran or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40 ° C Pressure: 68 kgf/cm ² [epoxy equivalent] Epoxy single The amount is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C 2105. [Solid viscosity of polymer solution] The solution viscosity (mPa × s) of the polymer solution was measured at 25 ° C using an E-type rotational viscometer. In the following, the compound represented by the formula (X) may be simply referred to as "compound (X)".

<Synthesis of polyorganosiloxane having epoxy group> [Synthesis Example 1] 70.5 g of 2-(3,4-epoxy ring) was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube. Hexyl)ethyltrimethoxydecane, 14.9 g of tetraethoxynonane, 85.4 g of ethanol and 8.8 g of triethylamine were mixed at room temperature. Then, 70.5 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and the mixture was stirred under reflux and reacted at 80 ° C for 2 hours. The reaction solution was concentrated, diluted with butyl acetate, and the operation was repeated twice, whereby triethylamine and water were distilled off to obtain a polymer solution containing polyorganosiloxane (SEp-1). When ¹ H-nuclear magnetic resonance (NMR) analysis was carried out, it was confirmed that no side reaction of the epoxy group was caused in the reaction. The polyorganosiloxane (SEp-1) had an Mw of 11,000 and an epoxy equivalent of 182 g/mole.

<Synthesis of Cinnamic Acid Derivative> The synthesis reaction chamber of the cinnamic acid derivative is carried out in an inert environment. [Synthesis Example 2] 19.2 g of 1-bromo-4-cyclohexylbenzene, 0.18 g of palladium acetate, 0.98 g of tris(2-methylphenyl)phosphine, and 32.4 g were mixed in a 500 mL three-necked flask equipped with a cooling tube. Triethylamine, 135 mL of dimethylacetamide. 7 g of acrylic acid was added to the mixed solution using a syringe and stirred. Further, the mixed solution was stirred while heating at 120 ° C for 3 hours. After confirming the completion of the reaction by Thin-Layer Chromatography (TLC), the reaction solution was cooled to room temperature. After separating the precipitate by filtration, the filtrate was poured into 300 mL of 1 N aqueous hydrochloric acid solution and the precipitate was recovered. The recovered precipitate was recrystallized with a 1:1 (mass ratio) solution of ethyl acetate and hexane, whereby 10.2 g of a compound represented by the following formula (M-1) (cinnamic acid derivative ( M-1)). [Chemistry 7]

<Synthesis of Photo-Oriented Polyorganooxane> [Synthesis Example 3] 11.3 g of the polyorganosiloxane (EPp-1) having an epoxy group obtained in Synthesis Example 1 was placed in a 100 mL three-necked flask. 13.3 g of n-butyl acetate, 1.7 g of the cinnamic acid derivative (M-1) obtained in Synthesis Example 2, and 0.54 g of an acryl-containing carboxylic acid (Aronix M-5300, East Asia Synthetic (manufactured by the company) and 0.9 g of tetrabutylammonium bromide were stirred at 80 ° C for 12 hours. After the completion of the reaction, 20 g of n-butyl acetate was further added, and the solution was washed with water three times, and then 20 g of n-butyl acetate was added thereto, and the solvent was distilled off so that the solid content concentration became 10% by mass. Thus, a n-butyl acetate solution containing a solid content concentration of 10% by mass of the polymer (S-1) as a photo-alignment polyorganosiloxane was obtained. The weight average molecular weight Mw of the polymer (S-1) was 18,000.

[Synthesis Example 4] 11.3 g of the polyorganooxynonane (SEp-1) having an epoxy group obtained in Synthesis Example 1, 13.3 g of n-butyl acetate, and 1.7 g were placed in a 100 mL three-necked flask. The cinnamic acid derivative (M-1) obtained in Synthesis Example 2 and 0.10 g of a quaternary amine salt (SAN APRO, UCAT18X) were stirred at 80 ° C for 12 hours. After the completion of the reaction, 20 g of n-butyl acetate was further added, and the solution was washed with water three times, and then 20 g of n-butyl acetate was added thereto, and the solvent was distilled off so that the solid content concentration became 10% by mass. Thereby, a n-butyl acetate solution containing a solid content concentration of 10% by mass of the polymer (S-2) as a photo-alignment polyorganosiloxane was obtained. The weight average molecular weight Mw of the polymer (S-2) was 17,000.

[Synthesis Example 5] A polyorganosiloxane having a cinnamic acid structure was obtained in accordance with the formulation described in Japanese Laid-Open Patent Publication No. Hei 9-278890. Specifically, boil a mixture of 0.05 ml of 4-fluorophenyl 4-enpropoxy cinnamic acid, 0.1 ml of methyl polyorganosiloxane, and a catalytic amount of platinum chloride in 100 ml of benzene. It was cooled for 10 hours and then diluted with methanol. The reaction product was filtered and washed with methanol. Thereafter, the polyorganosiloxane cinnamate is dried under vacuum at a temperature of from 50 ° C to 60 ° C until a fixed amount is obtained, and then pulverized in a vibrating mill, thereby obtaining a polymer (S-3) ). Further, when ¹ H-NMR analysis was carried out, it was confirmed that the double bond of the allyloxy group was not present in the obtained compound.

<Synthesis of Poly(meth)acrylate> [Synthesis Example 6] The monomer represented by the following formula (12) was dissolved in tetrahydrofuran according to the description in paragraph [0068] of International Publication No. 2013/081066. Polymerization was carried out by adding azobisisobutyronitrile (AIBN) as a polymerization initiator to obtain a polymer (Pac-4). [化8]

[Synthesis Example 7] 1 part by mass of 2,2'-azobis(isobutyronitrile) as a polymerization initiator and 180 parts by mass of diethylene glycol as a solvent were placed in a flask equipped with a cooling tube and a stirrer Methyl ethyl ether. Then, 70 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate and 30 parts by mass of 3-methyl-3-oxetanylmethyl methacrylate were added, and after nitrogen substitution, stirring was slowly started. . The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours, thereby obtaining a polymer solution containing a polymer (Pac-1) as an epoxy group-containing polymethacrylate. The solid content concentration of the obtained polymer solution was 32.8% by mass. The obtained polymer (Pac-1) had an Mn of 16,000.

[Synthesis Example 8] 100 parts by mass of the epoxy group-containing polymethacrylate (Pac-1) obtained in Synthesis Example 7 and 20 parts by mass of the acryloyl group-containing carboxylic acid (Aronix (Aronix) were charged. M-5300, manufactured by East Asia Synthetic Co., Ltd., 10 parts by mass of tetrabutylammonium bromide as a catalyst, and 150 parts by mass of propylene glycol monomethyl ether acetate as a solvent under a nitrogen atmosphere at 90 Stir at °C for 12 hours. After completion of the reaction, it was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and washed with water three times. The solution was concentrated, diluted with butyl acetate, and the operation was repeated twice to obtain a polymer solution containing a polymer (Pac-2) as a polymethacrylate containing an acryl group. The obtained polymer (Pac-2) had an Mn of 20,000. Further, the propylene glycol monomethyl ether acetate content in the obtained polymer solution was 20% by mass.

[Synthesis Example 9] 100 parts by mass of the epoxy group-containing polymethacrylate (Pac-1) obtained in Synthesis Example 7 and 20 parts by mass of the acryloyl group-containing carboxylic acid (Aronix (Aronix) were charged. M-5300, manufactured by East Asia Synthetic Co., Ltd., 20 parts by mass of the cinnamic acid derivative (M-1) obtained in Synthesis Example 2, 10 parts by mass of tetrabutylammonium bromide as a catalyst, 150 A part by mass of propylene glycol monomethyl ether acetate as a solvent was stirred at 90 ° C for 12 hours under a nitrogen atmosphere. After completion of the reaction, it was diluted with 100 parts by mass of propylene glycol monomethyl ether acetate, and washed with water three times. The solution was concentrated, diluted with butyl acetate, and the operation was repeated twice to obtain a polymerization of a polymer (Pac-3) containing polymethacrylate as a crosslinkable group and a photo-alignment group. Body solution. The obtained polymer (Pac-3) had an Mn of 25,000. Further, the propylene glycol monomethyl ether acetate content in the obtained polymer solution was 20% by mass.

<Synthesis of a styrene-maleimide-based copolymer> [Synthesis Example 10] In a 100 mL two-necked flask, the total mole number of the polymerized monomer was 43.1 mmol under nitrogen. 20 mol of the polymerizable monomer, represented by the following formula (MI-4), 10 mol parts of 4-vinylbenzoic acid, 30 mol parts of the following formula (MB-3) a compound and 40 moles of a compound represented by the following formula (MA-1), further adding 1.3 mmol of 2,2'-azobis(2,4-dimethyl group as a radical polymerization initiator) Valeronitrile), 2.2 mmol of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 25 ml of tetrahydrofuran as a solvent, and polymerized at 70 ° C for 5 hours. After reprecipitation in n-hexane, the precipitate was filtered and dried under vacuum at room temperature for 8 hours, whereby a polymer (Psm-1) was obtained. The weight average molecular weight Mw measured by polystyrene conversion by GPC was 30,000, and the molecular weight distribution Mw/Mn was 3. [Chemistry 9]

<Synthesis of Polylysine> [Synthesis Example 11] 19.61 g (0.1 mol) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) of 4,4'-diamino-2, 2'-Dimethylbiphenyl was dissolved in 367.6 g of N-methyl-2-pyrrolidone and allowed to react at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours, whereby 35 g of polylysine (PA-1) was obtained.

[Synthesis Example 12] 100 mol of the compound represented by the following formula (aa-1) and 100 mol of the compound represented by the following formula (da-1) were dissolved in cyclopentanone, and The reaction was carried out for 6 hours at 60 ° C to obtain a solution containing 15% by mass of poly-proline. The obtained polyaminic acid (polymer (PA-2)) had a weight average molecular weight Mw of 55,000. [Synthesis Example 13] 100 mol% of a compound represented by the following formula (aa-1) and 100 mol parts of a compound represented by the following formula (da-2) were dissolved in N-methyl-2- The pyrrolidone was reacted at 60 ° C for 6 hours to obtain a solution containing 15% by mass of poly-proline. The obtained polyaminic acid (polymer (PA-3)) had a weight average molecular weight Mw of 55,000. [Synthesis Example 14] 100 mol% of the compound represented by the following formula (aa-1) and 100 mol parts of the compound represented by the following formula (da-3) were dissolved in N-methyl-2- The pyrrolidone was reacted at 60 ° C for 6 hours to obtain a solution containing 15% by mass of poly-proline. The obtained polyaminic acid (polymer (PA-4)) had a weight average molecular weight Mw of 45,000. [化10]

<Synthesis of Polyvinyl Alcohol> [Synthesis Example 15] The ratio of x:y:z=70:18:12 (mol%) was obtained according to the description of paragraph [0101] of Japanese Patent No. 3907735 Modified polyvinyl alcohol (Pva-1) of the structural unit represented by the formula (16), the formula (17) and the formula (18), respectively. [11]

<Preparation and Evaluation of Liquid Crystal Alignment Film> [Example 1] 1. Preparation of liquid crystal alignment agent for optical anisotropic film formation Polymer-containing (S-1) obtained in Synthesis Example 3 as a polymer component The n-butyl acetate solution is equivalent to 30 parts by mass in terms of the polymer (S-1), and the polymer (Pac-1)-containing solution obtained in Synthesis Example 6 is converted into a polymer (Pac). -1) is equivalent to 70 parts by mass, and 3 parts by mass of aluminum tris(acetylpyruvate) as a catalyst (aluminum chelate A (W), manufactured by Kawaken Fine Chemical Co., Ltd.) And 1 part by mass of tris(p-tolyl) decyl alcohol as a hardening accelerator, to which n-butyl acetate (BA), methyl ethyl ketone (Methyl Ethyl Ketone, MEK), propylene glycol monomethyl as a solvent are added. Propylene Glycol Monomethyl Ether Acetate (PGMEA) and Ethyl Acetoacetate (EAA), the solid content concentration is 5% by mass, and the mass ratio of each solvent is BA: MEK: PGMEA: EAA = 40 :40:15:5 way to prepare. Then, the obtained solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (A-1).

2. Preparation of Transfer Laminate The prepared liquid crystal alignment agent (A-1) was applied onto a polyetheretherketone film as a support using a bar coater, and baked in an oven at 120 ° C. Bake for 2 minutes to form a coating film having a film thickness of 0.1 μm. Then, using a Hg-Xe lamp and a Glan-Taylor prism, the surface of the coating film was irradiated with a polarized ultraviolet ray of 313 nm in a bright line of 10 mJ/cm ² from the normal direction of the film surface to prepare a liquid crystal alignment film. Then, a polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was filtered using a 0.2 μm pore size filter, and coated on the surface of the liquid crystal alignment film using a bar coater. Then, after baking for 1 minute in an oven set to 50 ° C, the polymerizable liquid crystal was irradiated with non-polarized ultraviolet rays of 365 nm bright lines of 1,000 mJ/cm ² using an Hg-Xe lamp and hardened. The film thickness of the obtained film was 1.0 μm.

3. Evaluation of the peeling property The cross-cut test described in the above-mentioned transfer laminate was obtained by JIS Standard K5600-5-6 (International Standardization Organization (ISO) 2409). The peeling property of the optically anisotropic film with respect to the liquid crystal alignment film was evaluated. Regarding the cutting of the coating film, a lattice pattern of a right angle was cut into the coating film, and evaluation was performed in a state where the cutting reached the surface of the support. When the optically anisotropic film on the outermost surface is sufficiently adhered to the tape and completely peeled off, and the liquid crystal alignment film remains on the support, the peeling property of the optically anisotropic film with respect to the liquid crystal alignment film can be referred to as good. Specifically, the test results are performed in the following six categories. In the case of Category 0 or Category 1, it is determined that the peelability is "good", and in the case of Category 2 or Category 3, it is determined that the peelability is "OK". In the case of Category 4 or Category 5, it is judged that the peeling property is "poor". In this embodiment, the classification is 0, and the peelability is "good". Classification 0: The cut edges were completely smooth, and there was no peeling of the alignment film in the grid of any of the lattices, and only the optically anisotropic film was peeled off. Classification 1: At the intersection of the cuts, the alignment film together with the optically anisotropic film produces a small peeling. Among them, in the cross-cut portion, the affected portion is clearly below the state of 5%. Class 2: The alignment film is peeled off along the edge of the cut, or peeled off together with the optically anisotropic film at the intersection, or both. Among them, in the cross-cut portion, the affected portion is clearly more than 5% but less than 15%. Category 3: The alignment film produces a large peeling together with the optically anisotropic film locally or entirely along the edge of the cut, or many portions of the mesh are partially or entirely peeled off together with the optically anisotropic film, or The status of both. Among them, in the cross-cut portion, the affected portion is clearly more than 15% but less than 35%. Class 4: the alignment film produces a large peeling together with the optically anisotropic film locally or entirely along the edge of the cut, or a plurality of meshes are partially or entirely peeled off together with the optically anisotropic film, or The status of both. Among them, in the cross-cut portion, the affected portion is clearly more than 35% but less than 65%. Category 5: Produces a state of large spalling that is also not classified as Category 4.

4. Evaluation of the transparency The optical anisotropic film formed on the liquid crystal alignment film by the "2. Preparation of the laminated body for transfer" is applied to the glass substrate by applying an adhesive to the glass substrate. on. The transparency of the optically anisotropic film after transfer was evaluated by measuring the haze (HAZE) of the optically anisotropic film after transfer. The measurement was performed using a spectrophotometer (manufactured by Tokyo Denshoku Co., Ltd.). The lower the haze value, the better the transparency. Specifically, when the haze value is 2% or less, it is judged that the transparency is "good (A)", and when the haze value is more than 2% and is 4% or less, it is judged that the transparency is "may" ( B)", when the haze value is more than 4%, it is judged that the transparency is "defective (C)". The transparency of this embodiment is "good (A)".

5. Evaluation of liquid crystal alignment property With respect to the optically anisotropic film transferred onto the glass substrate, the liquid crystal alignment property was observed by a visual observation and a polarizing microscope under crossed nicols. When the liquid crystal alignment property was observed by a visual observation and the abnormal region was not observed by a polarizing microscope, it was evaluated as "good (A)", and the alignment was observed by visual observation but observed by a polarizing microscope. The case of the abnormality domain was evaluated as "(B)", and the abnormality of the liquid crystal alignment property was observed by visual observation as "defective (C)". As a result, in this example, the liquid crystal alignment property was evaluated as "good (A)".

6. Evaluation of Surface Roughness of Liquid Crystal Alignment Film The prepared liquid crystal alignment agent (A-1) was applied onto a glass substrate using a spinner, and prebaked for 1 minute using a hot plate at 100 ° C to form a film thickness of 0.1. Μm coating film. Then, using a Hg-Xe lamp and Glan-Taylor, the surface of the coating film was irradiated with a polarized ultraviolet ray of 313 nm bright line of 10 mJ/cm ² from the normal line of the substrate surface to prepare a liquid crystal alignment film. The obtained liquid crystal alignment film was observed by an atomic force microscope (AFM) to measure the center average roughness (Ra). In the case where Ra is less than 2.0 nm, the surface roughness is "good (A)", when it is 2.0 nm or more and less than 5.0 nm, it is "B (B)", and when it is 5.0 nm or more, it is "Bad ( C)" to proceed. The surface roughness of this example was "good (A)".

[Example 2 to Example 9, Example 11, and Example 12] The liquid crystal alignment agent (A-1) was prepared in the same manner as in the first embodiment except that the composition of the liquid crystal alignment agent was changed as described in the following Table 1. The liquid crystal alignment agent (A-2) to the liquid crystal alignment agent (A-11) were prepared in the same manner. In the same manner as in Example 1, except that the liquid crystal alignment agent (A-2) to the liquid crystal alignment agent (A-11) were used instead of the liquid crystal alignment agent (A-1), as shown in the following Table 1, various evaluations were carried out in the same manner as in Example 1. . [Example 10] Various evaluations were carried out in the same manner as in Example 9 except that the rubbing treatment was performed in the direction orthogonal to the longitudinal direction of the film instead of the photo-alignment treatment.

[Comparative Example 1] A liquid crystal alignment agent (R-1) was prepared in the same manner as in the method for producing a liquid crystal alignment agent (A-1) in Example 1, except that the composition of the liquid crystal alignment agent was changed as described in the following Table 1. . In addition, the liquid crystal alignment agent (R-1) is used in place of the liquid crystal alignment agent (A-1), and rubbing treatment is performed in a direction orthogonal to the longitudinal direction of the film instead of the optical alignment treatment, and the same as in the first embodiment. Implement and conduct various evaluations. [Comparative Example 2] A liquid crystal alignment agent (R-2) was prepared in the same manner as in the method for producing a liquid crystal alignment agent (A-1) in Example 1, except that the composition of the liquid crystal alignment agent was changed as described in the following Table 1. . In addition, the liquid crystal alignment agent (R-2) was used instead of the liquid crystal alignment agent (A-1), and the surface of the coating film formed using the liquid crystal alignment agent was irradiated with 10,000 J/m ² from the normal direction of the substrate surface. Various evaluations were carried out in the same manner as in Example 1 except for the polarized ultraviolet rays of the bright line of 254 nm. [Comparative Example 3] A liquid crystal alignment agent (R-3) was prepared in the same manner as in the method for producing a liquid crystal alignment agent (A-1) in Example 1, except that the composition of the liquid crystal alignment agent was changed as described in the following Table 1. . In addition, various evaluations were performed in the same manner as in Example 1 except that the liquid crystal alignment agent (R-3) was used instead of the liquid crystal alignment agent (A-1).

[Table 1]

The numerical value of the "mixing amount" in Table 1 indicates the blending ratio (parts by mass) of 100 parts by mass of the total of the polymer components used in the preparation of the liquid crystal alignment agent. In Table 1, the abbreviations of the compounds are as follows. <Catalyst> B-1: Aluminum tris(acetylpyruvate) (aluminum chelate A (W), manufactured by Kawaken Fine Chemical) <hardening accelerator> K-1: tris(p-toluene) Base stanol K-2: trimellitic acid K-3: 4,4'-methylenebis(N,N-diglycidylaniline) <solvent> BA: n-butyl acetate MEK: methyl b Ketone PGMEA: propylene glycol monomethyl ether acetate EAA: ethyl acetate ethyl acetate EDM: diethylene glycol ethyl methyl ether CHN: cyclohexanone CPN: cyclopentanone PGME: propylene glycol monomethyl ether THF: tetrahydrofuran WT: Distilled water MEOH: methanol NMP: N-methyl-2-pyrrolidone BC: γ-butyrolactone The evaluation results of Examples 1 to 12 and Comparative Examples 1 to 3 are summarized in Table 2 below. .

[Table 2]

It is clear from Table 2 that in the examples 1 to 10, the surface roughness of the liquid crystal alignment film and the transparency of the optically anisotropic film transferred onto the glass substrate were evaluated as "A" or "B". Further, the evaluation of the peeling property of the optically anisotropic film with respect to the liquid crystal alignment film was classified into 0 to 2 . In the above, when Example 9 in which the photo-alignment treatment was performed was compared with Example 10 in which the rubbing treatment was carried out, the surface roughness of Example 9 was small, and good results were obtained. Further, in Example 7 and Example 8 using a polymethacrylate having a polymerizable group as the polymer [A], the peeling was performed as compared with Example 9 using a polymethacrylate having no polymerizable group. The evaluation of properties, transparency, and liquid crystal alignment was good. On the other hand, the peelability of the optically anisotropic film of Comparative Example 1, the surface roughness of the liquid crystal alignment film, and the transparency of the optically anisotropic film after peeling were all inferior to those of the examples. Further, in the comparative example (Comparative Example 2) containing no polymer [A], the optically anisotropic film was inferior in peelability from the examples, and the liquid crystal alignment property was "poor". Further, when an example of using a poly-proline having a photo-alignment group is observed, it has a light alignment in the main chain as compared with Comparative Example 3 used for the polymer PA-4 having a photo-alignment group in the side chain. The peelability and liquid crystal alignment of the examples of the polymer-based polymer PA-2 and the polymer PA-3 (Example 11 and Example 12) were evaluated as good.

(Use as a circularly polarizing plate) A laminated body was produced in the same manner as in "2. Production of laminated body for transfer" in Example 1. Further, the thickness of the polymerizable liquid crystal layer was adjusted to 1/4l. Then, an adhesive is applied to the polarizing plate HLC2-2518 manufactured by SANRITZ Co., Ltd., and the laminated body is formed at a 45-degree angle with the absorption axis of the polarizing plate and the absorption axis of the polarizing plate. Fit it together. Then, the support and the alignment film are peeled off to manufacture a circularly polarizing plate. For the obtained circular polarizing plate, an adapter ARV-474 was mounted on a spectrophotometer V-550 (manufactured by JASCO Corporation) in the wavelength range of 380 nm to 780 nm from the normal direction of the circular polarizing plate surface. The specular reflectance at an exit angle of 5° at an incident angle (polar angle) of 5° was measured, and as a result, it was found to be 0.2% and had a good antireflection function.

As described above, it is clear that by using the liquid crystal alignment agent containing the polymer [A], the surface roughness of the liquid crystal alignment film can be made small, the peeling property with the optical anisotropic film is good, and the optical orientation after peeling can be obtained. A liquid crystal alignment film having a good transparency of a foreign film. Therefore, it is useful for forming an optically anisotropic film (liquid crystal layer) on the surface of a liquid crystal alignment film formed using a liquid crystal alignment agent containing the polymer [A], and the obtained laminate The optically anisotropic film is adhered to the adherend and then peeled off to obtain a structure in which only the optically anisotropic film is transferred onto the adherend.

10‧‧‧Layer

11‧‧‧Support

12‧‧‧Liquid alignment film

13‧‧‧ Optical anisotropic film

21‧‧‧Adhesive body

22‧‧‧Next layer

23‧‧‧Optical compensation film

FIG. 1 is a schematic view showing a method of forming an optical compensation film.

Claims (14)

A laminate having a support, a liquid crystal alignment film formed on the support, and a transfer film having an optical compensation function formed on the liquid crystal alignment film, wherein the liquid crystal alignment The film is formed using a liquid crystal alignment agent containing a polyorganosiloxane, a styrene-maleimide copolymer, a (meth)acrylic polymer, and a polyamic acid. At least one of the group consisting of the polymer [A] having a photo-alignment group (wherein, in the case of poly-proline, a photo-alignment group in the main chain). The laminate according to claim 1, wherein the transfer film is an optically anisotropic film containing a liquid crystal compound, and the laminate is for using the optical bodies of the laminate The optically anisotropic film is formed on the adherend by transferring the film to the adherend. The laminate according to claim 1 or 2, wherein the polymer [A] has a photo-alignment group selected from a cinnamic acid-containing structure containing cinnamic acid or a derivative thereof as a basic skeleton. And a group consisting of azobenzene-containing groups containing azobenzene or a derivative thereof as a basic skeleton. The laminate according to any one of the above-mentioned claims, wherein the photo-alignment group of the polymer [A] is a group represented by the following formula (1); (In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a cyano group; and R ³ is a halogen atom; An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a cyano group; a is an integer of 0 to 4; and when a is 2 or more, a plurality of R ³ may be the same or may be the same Different; X ¹ is an oxygen atom, a sulfur atom or -NR ⁸ - (wherein R ⁸ is a hydrogen atom or a monovalent organic group); "*" means a bonding bond). The laminate according to any one of claims 1 to 4, which has polymerization in the same molecule as the polymer [A] or in a molecule different from the polymer [A]. Sexual basis. A liquid crystal alignment agent for forming a transfer film having an optical compensation function, and the liquid crystal alignment agent contains a copolymer selected from the group consisting of polyorganosiloxanes, styrene-maleimide copolymers, a polymer [A] having at least one of a group consisting of an acrylic polymer and a polyamic acid and having a photo-alignment group (wherein, in the case of poly-proline, it has a main chain) Photoalignment basis). The liquid crystal alignment agent according to claim 6, wherein the transfer film is an optically anisotropic film containing a liquid crystal compound, and the liquid crystal alignment agent is used for forming a self-supporting body, formed on a liquid crystal alignment film on the support and a laminate of the optically anisotropic film formed on the liquid crystal alignment film to transfer the optically anisotropic film to the liquid crystal alignment film on the adherend . A liquid crystal alignment film which is a liquid crystal alignment film provided in a laminate, the laminate having a support, a liquid crystal alignment film formed on the support, and an optical compensation function formed on the liquid crystal alignment film The transfer film is formed using the liquid crystal alignment agent as described in claim 6 or 7. A method for producing a laminate, wherein the laminate has a support, a liquid crystal alignment film formed on the support, and a transfer film having an optical compensation function formed on the liquid crystal alignment film, and the laminate The method for producing a body comprising: applying a liquid crystal alignment agent according to claim 6 or 7 to the support to form a coating film; and applying light to the coating film to impart liquid crystal An alignment capability, whereby a step of forming a liquid crystal alignment film on the support; and a step of forming the optically anisotropic film on the liquid crystal alignment film. The method for producing a laminated body according to claim 9, wherein the coating film is formed by heating a substrate surface coated with the liquid crystal alignment agent at 150 ° C or lower. A method of forming an optical compensation film, which is a method of forming an optical compensation film on an adherend, and the method of forming the optical compensation film comprises: according to any one of items 1 to 5 of the patent application scope The transfer film of the laminated body described above is transferred onto the adherend. A method of producing a polarizing film with a retardation film, wherein the method for producing a polarizing film with a retardation film, comprising: the layered body according to any one of claims 1 to 5 The step of transferring the transfer film onto the polarizing film. A polarizing film having a retardation film, which is obtained by transferring a transfer film of a laminate according to any one of the first to fifth aspects of the invention to a polarizing film. A method of manufacturing a liquid crystal display device, wherein the method for fabricating a liquid crystal display device comprises: a step of constructing a liquid crystal cell having a pair of substrates disposed oppositely and a liquid crystal layer disposed between the pair of substrates; And a step of transferring a transfer film of the laminate according to any one of the first to fifth aspects of the invention to the outside of at least one of the pair of substrates of the liquid crystal cell.