TWI822746B - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

An object of the present invention is to provide a cured film-forming composition that forms a cured film having excellent liquid crystal alignment and adhesion, its cured film, an optical film, an alignment material, and a retardation material formed using the cured film. The solution is to form a cured film containing (A) a polymer with photoalignment groups, hydroxyl groups, and polymerizable groups containing C=C double bonds, (B) cross-linking agents, and (C) cross-linking catalysts. Composition, cured film formed from the cured film forming composition, optical film formed using the cured film, alignment material, and retardation material.

Description

Cured film forming composition, alignment material and retardation material

The present invention relates to a cured film-forming composition, a cured film, an optical film, an alignment material, and a retardation material that form a cured film that aligns liquid crystal molecules. The present invention particularly relates to patterned phase difference materials used in 3D displays using circularly polarized glasses, phase difference materials used in circularly polarizing plates used as anti-reflective films in organic EL displays, and useful in making the phase difference materials. Cured film forming compositions, cured films, optical films and alignment materials of poor materials.

In the case of 3D displays using circularly polarized glasses, phase difference materials are usually placed on display elements that form images, such as liquid crystal panels. This phase difference material has two types of phase difference regions with different phase difference characteristics arranged in a plural and regular manner, forming a patterned phase difference material. In the following, in this specification, a retardation material patterned in such a manner that a plurality of retardation regions with different retardation characteristics are arranged is called a patterned retardation material.

A patterned retardation material can be produced by optically patterning a retardation material composed of polymerizable liquid crystal, as disclosed in Patent Document 1, for example. Optical patterning of phase difference materials composed of polymeric liquid crystals utilizes photo-alignment technology known in the formation of alignment materials for liquid crystal panels. That is, a coating film composed of a photo-alignment material is provided on a substrate, and two types of polarized light with different polarization directions are irradiated onto the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different alignment control directions of liquid crystal are formed. A solution phase difference material containing polymerizable liquid crystal is coated on the photo-alignment film to realize alignment of the polymerizable liquid crystal. Afterwards, the aligned polymeric liquid crystal is hardened to form a patterned retardation material.

The anti-reflective film of the organic EL display is composed of a linear polarizing plate and a 1/4 wavelength phase difference plate. The external light directed towards the panel surface of the image display panel is converted into linearly polarized light by the linear polarizing plate, and then 1/4 wave retardation plate is used. The 4-wavelength phase difference plate converts circularly polarized light. Here, the circularly polarized external light is reflected from the surface of the image display panel, but the rotation direction of the polarizing surface is reversed during this reflection. As a result, the reflected light is reversed when it arrives, and is converted by the 1/4 wavelength phase difference plate into linearly polarized light in the direction of being blocked by the linear polarizing plate, and then is blocked by the linear polarizing plate. As a result, Emission to the outside is significantly suppressed.

Regarding this 1/4-wavelength retardation plate, Patent Document 2 proposes that a 1/4-wavelength retardation plate is constituted by combining a 1/2-wavelength plate and a 1/4-wavelength plate, and the optical structure is configured with reverse dispersion characteristics. thin film method. In the case of this method, a liquid crystal material with positive dispersion characteristics can be used in a wide wavelength band for color image display, and an optical film can be formed by using reverse dispersion characteristics.

Furthermore, in recent years, liquid crystal materials having reverse dispersion characteristics that can be applied to the retardation layer have been proposed (Patent Documents 3 and 4). According to the liquid crystal material with such reverse dispersion characteristics, the retardation layer is composed of a single layer, instead of combining the 1/2-wavelength plate and the 1/4-wavelength plate, the 1/4-wavelength retardation plate is composed of two retardation layers. , can ensure reverse dispersion characteristics, thereby realizing an optical film that can ensure a desired phase difference in a wide wavelength band with a simple structure.

In order to align the liquid crystal, an alignment layer is used. Known methods for forming the alignment layer include the rubbing method and the photo-alignment method. The photo-alignment method is useful in a quantitative alignment process that does not cause static electricity or dust, which is a problem with the rubbing method.

When forming an alignment material using a photo-alignment method, known materials with photo-alignment properties that can be used include acrylic resins and polyimide resins that have photodimerization sites such as cinnamyl groups and chalcone groups in their side chains. . It has been reported that these resins can exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment properties) by irradiating polarized UV (refer to Patent Documents 5 to 7).

In addition, the alignment layer requires not only liquid crystal alignment ability but also solvent resistance. For example, the alignment layer may be exposed to heat or solvent during the manufacturing process of the retardation material. When the alignment layer is exposed to solvent, there is a risk that the liquid crystal alignment energy will be significantly reduced.

Therefore, for example, in Patent Document 8, in order to obtain stable liquid crystal alignment ability, a liquid crystal alignment agent containing a polymer component having a structure capable of cross-linking reaction by light and a structure capable of cross-linking by heat is proposed, and a liquid crystal alignment agent containing A liquid crystal alignment agent having a polymer component having a structure that can be cross-linked by light and a compound having a structure that can be cross-linked with heat.

In addition, the alignment layer is required to have good adhesion with the liquid crystal layer. When the adhesion between the alignment layer and the liquid crystal layer formed thereon is insufficient, for example, during the winding step in manufacturing the retardation film, the liquid crystal layer may peel off. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2005-49865 [Patent Document 2] Japanese Patent Application Publication No. 10-68816 [Patent Document 3] U.S. Patent No. 8119026 Specification [Patent Document 4] Japanese Patent Application Publication No. 2009-179563 [Patent Document 5] Japanese Patent No. 3611342 [Patent Document 6] Japanese Patent Application Publication No. 2009-058584 [Patent Document 7] Japanese Patent Publication No. 2001-517719 [Patent Document 8] Japanese Patent No. 4207430

[Problem to be solved by the invention]

The present invention is based on the above insights or research results. That is, an object of the present invention is to provide a cured film for use in forming a cured film of an alignment material that has excellent solvent resistance, can align polymerizable liquid crystal with high sensitivity, and has excellent adhesion to the liquid crystal layer. form composition. Furthermore, an object of the present invention is to provide an optical film having the above-mentioned cured film, and an alignment material and a retardation material formed using the cured film or optical film.

Other objects and advantages of the present invention will become apparent from the following description. [Means used to solve problems]

A first aspect of the present invention relates to a cured film forming composition containing (A) A polymer having a photoalignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond, (B) cross-linking agent, and (C) Cross-linking catalyst. In the first aspect of the present invention, the photo-alignment group of component (A) is preferably a functional group having a structure of photodimerization or photoisomerization. In the first aspect of the present invention, the photo-alignment group of component (A) is preferably a group having a cinnamonyl group or an azobenzene structure. In the first aspect of the present invention, it is preferred that the polymer further contains (D) a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a amide group, an amine group, and an alkoxysilyl group. In the first aspect of the present invention, the polymer of component (A) preferably contains a structural unit having a hydroxyl group and a structural unit having a polymerizable group containing a C=C double bond, and the ratio of the structural unit having a hydroxyl group is , relative to 100 mol% of all structural units of the polymer, is 20 mol% or more, and the proportion of the structural units having polymerizable groups containing C=C double bonds is relative to the polymer. In terms of 100 mol% of all structural units, it is more than 5 mol%. In the first aspect of the present invention, the cured film forming composition preferably contains 5 to 500 parts by mass of component (B) based on 100 parts by mass of component (A). In the first aspect of the present invention, the cured film forming composition preferably contains 0.01 to 20 parts by mass of component (C) based on 100 parts by mass of component (A).

A second aspect of the present invention relates to a cured film obtained from the cured film forming composition of the first aspect of the present invention.

A third aspect of the present invention relates to an optical film having a cured film obtained from the cured film-forming composition of the first aspect of the present invention.

A fourth aspect of the present invention relates to an alignment material, characterized by being formed using the cured film of the second aspect of the present invention.

A fifth aspect of the present invention relates to a retardation material, characterized by being formed using the cured film of the second aspect of the present invention. [Effects of the invention]

According to the present invention, it is possible to provide a cured film having excellent solvent resistance, capable of aligning polymerizable liquid crystal with high sensitivity, excellent adhesion to the liquid crystal layer, and a cured film-forming composition suitable for its formation. Furthermore, according to the present invention, it is possible to provide an optical film having the above-mentioned cured film, and an alignment material and a retardation material formed using the cured film or the optical film.

As described above, there is a demand for a cured film (alignment material) that has excellent solvent resistance, can align polymerizable liquid crystal with high sensitivity, and has excellent adhesion to the liquid crystal layer. In addition, a cured film forming composition suitable for forming a cured film (alignment material) with such properties is in demand.

In order to respond to the above request, the present inventors conducted in-depth research and found that a cured film obtained from a cured film-forming composition having a specific composition can be used as a cured film that has excellent solvent resistance and can align polymeric liquid crystals with high sensitivity. , an alignment material with excellent adhesion to the liquid crystal layer.

Hereinafter, the cured film forming composition of the present invention will be described in detail while listing specific examples of components and the like. In addition, the cured film and alignment material of the present invention using the cured film forming composition of the present invention, as well as the retardation material and liquid crystal display element formed using the alignment material will be described.

＜Cure film forming composition＞ The cured film forming composition of the present invention contains a polymer having a photoalignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond as the component (A), a cross-linking agent as the component (B), and (C). ) component of the cross-linking catalyst. Moreover, the polymer which has at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a amide group, an amino group, and an alkoxysilyl group may contain (D) component. Furthermore, other additives may be included as long as the effects of the present invention are not impaired. Furthermore, a solvent may be included. Details of each ingredient are explained below.

[(A) ingredient] Component (A) in the cured film forming composition of the present invention is a polymer having a photo-alignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond. That is, component (A) is a component that imparts photo-alignment properties to the cured film obtained from the cured film-forming composition of the present invention. In this specification, component (A) is also referred to as a photo-alignment component.

The component (A) contained in the cured film forming composition of the present invention is preferably an acrylic copolymer having a photo-alignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond.

In the present invention, an acrylic copolymer refers to a copolymer obtained by polymerizing monomers having unsaturated double bonds such as acrylate, methacrylate, and styrene.

The component (A) is an acrylic copolymer having a photoalignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond (hereinafter also referred to as a specific copolymer), as long as it is an acrylic copolymer having such a structure , the skeleton of the main chain of the polymer constituting the acrylic copolymer and the types of side chains are not particularly limited.

Examples of the photoalignment group include cinnamyl group, chalcone group, coumarin group, and anthracenyl group. Among these, cinnamyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity. More preferred cinnamyl groups and substituents containing a cinnamyl group structure include structures represented by the following formula [1] or formula [2]. Furthermore, in this specification, the benzene ring in the cinnamonyl group is the base of the naphthalene ring, and is also included in the "cinnamonyl group" and "substituents containing the cinnamonyl group structure".

In the above formula [1], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In this case, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.

In the above formula [2], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, alkyl groups, phenyl groups, biphenyl groups, and cyclohexyl groups with carbon atoms of 1 to 18 can also be formed through covalent bonds, ether bonds, ester bonds, amide bonds, urea bonds, and urethane bonds. , amine bond, carbonyl group, or one or more types of bonds selected from a combination thereof, and there are multiple types of bonds.

In the above formula [1] and formula [2], A represents any one of formula [A1], formula [A2], formula [A3], formula [A4], formula [A5], and formula [A6].

In the above formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6], R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group.

The hydroxyl group is a site bonded to the cross-linking agent of component (B) by heating. Furthermore, the polymer of the present invention may have thermally cross-linkable moieties other than hydroxyl groups. Specific examples include carboxyl groups, amide groups, amine groups, alkoxysilyl groups, and the like. In the polymer of component (A), the proportion of the structural unit having a hydroxyl group is preferably 20 mol% or more relative to 100 mol% of all structural units of the polymer. By making the content 20 mol% or more, the cured film obtained from the cured film-forming composition of the present invention can improve the efficiency of the photoreaction for photoalignment and can have excellent alignment sensitivity. Here, when the polymer of component (A) contains two or more structural units having a hydroxyl group, the ratio of the structural units having a hydroxyl group is expressed as the ratio of the structural units having a hydroxyl group per 100 moles of all structural units of the polymer. The number of moles in the unit) × (the number of hydroxyl groups contained in the structural unit).

The acrylic copolymer of component (A) preferably has a weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight exceeds 200,000 and is too large, the solubility in solvents may be reduced and the operability may be reduced. On the other hand, if the weight average molecular weight is less than 3,000 and is too small, the hardening may be insufficient during thermal hardening and the solvent tolerance may be reduced. Or the heat resistance is reduced.

(A) A method for producing an acrylic copolymer having a photo-alignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond as components can be exemplified by the following method.

Method 1 for producing component (A): after copolymerizing a monomer having a photodimerization site and a monomer having an epoxy group, the epoxy group of the resulting copolymer is then copolymerized with a monomer having a carboxyl group and containing C= A method for reacting compounds with polymerizable groups of C double bonds.

Method 2 for producing component (A) is to copolymerize a monomer with a photodimerization site and a monomer with a carboxyl group, and then combine the carboxyl group of the resulting copolymer with an epoxy group and a C=C double A method for reacting compounds with polymeric groups bonded to them.

Examples of the monomer having a photodimerization site include monomers having a cinnamyl group, a chalcone group, a coumarin group, an anthracene group, and the like. Among these, a monomer having a cinnamonyl group is particularly preferred because of its high transparency in the visible light region and high photodimerization reactivity.

Among them, monomers containing a cinnamyl group having a structure represented by the above formula [1] or formula [2] and a substituent of the cinnamyl group structure are particularly preferred. Specific examples of such monomers include monomers represented by the following formula [3] or formula [4].

In the above formula [3], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In this case, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group. L ¹ and L ² independently represent a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond.

In the above formula [4], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, alkyl groups, phenyl groups, biphenyl groups, and cyclohexyl groups with 1 to 18 carbon atoms can also be bonded through covalent bonds, ether bonds, ester bonds, amide bonds, and urea bonds.

In the above formulas [3] and [4], X ³ and X ⁵ independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring, and a divalent aliphatic ring. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

In the above formula [3] and formula [4], X ⁴ represents a polymerizable group. Specific examples of the polymerizable group include an acrylyl group, a methacrylamide group, a styryl group, a maleimide group, an acrylamide group, and a methacrylamide group.

In the above-mentioned formula [3] and formula [4], A represents formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6] in the same manner as above. Either.

Monomers having a polymerizable group and a carboxyl group containing a C=C double bond, such as acrylic acid, methacrylic acid, crotonic acid, and mono-(2-(acryloxy)ethyl) phthalate , mono-(2-(methacryloxy)ethyl) phthalate, mono-(2-(acryloxy)ethyl) hexahydrophthalate, mono -(2-(methacryloxy)ethyl)hexahydrophthalate, mono-(2-(acryloxy)ethyl)succinate, mono-(2-( Methacryloxy)ethyl)succinate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide Amine and omega-carboxy-polycaprolactone mono(meth)acrylate. These monomers can be used, for example, as "LIGHT ESTER HO-MS", "LIGHT ACRYLATE HOA-MS(N)", "LIGHT ACRYLATE HOA-HH(N)" and "LIGHT ACRYLATE HOA-MPL(N)" (above, trade name manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-5300, Aronix M-5400 (above, manufactured by Toa Gosei Co., Ltd., trade name), A-SA, SA (above, Shin Nakamura Chemical Industrial (stock) system, trade name) and commercially available.

Monomers having a polymerizable group and an epoxy group containing a C=C double bond include, for example, glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl methacrylate glycidyl ether, and allyl glycidyl ether. Glyceryl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0]heptane , 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide, etc.

Here, in the production of the polymer of component (A), at least one of the monomer having an epoxy group and the monomer having a carboxyl group as the raw material is preferably selected from the group consisting of a polymerizable group and an epoxy group and a carboxyl group. There is a spacer between the bases. By selecting such raw materials, the adhesiveness of the cured film of the present invention obtained to the liquid crystal layer becomes better.

The preferred structure of the monomer having a spacer group and a carboxyl group is either of the following (SC-1) and (SC-2). In the ^formula , amide group, etc. L ¹ represents a covalent bond, ether bond, ester bond, amide bond, urea bond or urethane bond. Q ¹ and Q ³ each independently represent an alkylene group having 2 to 10 carbon atoms, and Q ² represents a divalent group having a structure derived from a dicarboxylic anhydride. n represents a natural number from 1 to 10.

Such a monomer having a spacer group and a carboxyl group is preferably mono-(2-(acryloxy)ethyl) phthalate or mono-(2-(methacryloxy)) Ethyl) phthalate, mono-(2-(acryloxy)ethyl) hexahydrophthalate, mono-(2-(methacryloxy)ethyl ) Hexahydrophthalate, mono-(2-(acryloxy)ethyl)succinate, mono-(2-(methacryloxy)ethyl)succinate and Omega-carboxy-polycaprolactone mono(meth)acrylate. Furthermore, a polyfunctional acrylate having a carboxyl group is also preferred. Commercially available products include "LIGHT ESTER HO-MS", "LIGHT ACRYLATE HOA-MS(N)", "LIGHT ACRYLATE HOA-HH (N)" and "LIGHT ACRYLATE HOA-MPL(N)" (the above, Commercially available are Aronix M-5300, Aronix M-5400 (above, manufactured by Kyoeisha Chemical Co., Ltd., trade name), Aronix M-5300, and Aronix M-5400 (above, manufactured by Toa Gosei Co., Ltd., trade name).

The preferred structure of the monomer having a spacer group and an epoxy group is represented by the following (SE-1). In the ^formula , amide group, etc. L ¹ represents a covalent bond, ether bond, ester bond, amide bond, urea bond or urethane bond. Q ¹ represents an alkylene group having 2 to 10 carbon atoms.

Examples of such monomers having a spacer group and an epoxy group include 4-hydroxybutyl methacrylate glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- Vinyl benzyl glycidyl ether, etc.

The monomer having a polymerizable group containing a C=C double bond and a carboxyl group used to graft the epoxy group of the polymer is also preferably a polyfunctional acrylate having a carboxyl group represented by the following (SC-3) . In the ^formula , amide group, etc. L ¹ represents a covalent bond, ether bond, ester bond, amide bond, urea bond or urethane bond. Q ⁴ represents (m+1)-valent organic radical, and m represents a natural number from 2 to 10.

Such compounds can be used as those commercially available as Aronix M-510 and M-520 (above, trade names manufactured by Toagosei Co., Ltd.).

The usage amount of the monomer having a photodimerization site and the monomer having an epoxy group used to obtain the specific copolymer according to Production Method 1 is based on the total amount of all monomers used to obtain the specific copolymer, which is less than Preferably, the monomer having a photodimerization site is 40% to 95% by mass, and the monomer having an epoxy group is 5% to 60% by mass. By setting the content of the monomer having a photodimerization site to 40% by mass or more, high sensitivity and good liquid crystal alignment can be provided. On the other hand, by being 95 mass % or less, sufficient thermosetting properties can be provided, and high sensitivity and good liquid crystal alignment can be maintained.

In order to obtain a specific copolymer in accordance with Production Method 2, the usage amounts of the monomer having a photodimerization site and the monomer having a carboxyl group used are the above-mentioned monomers having a photodimerization site and the monomer having an epoxy group. The usage amount of the monomer with epoxy group.

In addition, in the cured film forming composition of the present invention, when obtaining a polymer as a precursor of a specific copolymer, it may be used in combination with a polymer having a photodimerization site, an epoxy group and a carboxyl group (hereinafter also referred to as a specific copolymer). A monomer copolymerized with any monomer having a non-reactive functional group (hereinafter also referred to as a monomer having a non-reactive functional group).

Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like. Specific examples of the above monomers are listed below, but the present invention is not limited to these.

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthracenyl methyl acrylate, phenyl acrylate, glycidyl acrylate, and 2 acrylate. ,2,2-trifluoroethyl, tert-butyl acrylate, cyclohexyl acrylate, isocamphenyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxy acrylate Ethyl acrylate, tetrahydrofuran methyl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-acrylate Tricyclodecyl ester, and 8-ethyl-8-tricyclodecyl acrylate, etc.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, and methacrylic acid. Anthryl methyl ester, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, methacrylic acid Isocamphenyl, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofuran methyl methacrylate, 3-methacrylate Methoxybutyl ester, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl methacrylate methyl-8-tricyclodecyl ester, and 8-ethyl-8-tricyclodecyl methacrylate, etc.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-vinyl-7-oxabicyclo [4.1.0 ]Heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide, etc.

Examples of the above-mentioned styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

The method of obtaining a polymer as a precursor of a specific copolymer used in the cured film forming composition of the present invention is not particularly limited. For example, a specific copolymer having a photodimerization site, an epoxy group, and a carboxyl group coexists. It is obtained by polymerizing a monomer with a functional group, a monomer with a non-reactive functional group as desired, and a polymerization initiator in a solvent at a temperature of 50°C to 110°C. At this time, the solvent used is not particularly limited as long as it can dissolve a monomer having a specific functional group, a monomer having a non-reactive functional group as desired, a polymerization initiator, etc. Specific examples include solvents described below as solvents.

The reaction product of a polymer having an epoxy group in the side chain and a compound having a specific carboxyl group and a polymerizable group containing a C=C double bond can be obtained by mixing a polymer having an epoxy group with The compound of a specific carboxyl group and a polymerizable group containing a C=C double bond is preferably synthesized by reacting in the presence of a catalyst, preferably in an appropriate organic solvent. The ratio of the compound having a carboxyl group and a polymerizable group containing a C=C double bond used in the reaction is preferably 0.01 per mole of epoxy group contained in the polymer having an epoxy group. ~0.9 mole, more preferably 0.05~0.8 mole, and more preferably 0.1~0.7 mole.

The reaction product of a polymer having a carboxyl group in the side chain and a compound having a specific epoxy group and a polymerizable group containing a C=C double bond can be obtained by reacting a polymer having a carboxyl group with a specific ring The compound of an oxygen group and a polymerizable group containing a C=C double bond is preferably synthesized by reacting in the presence of a catalyst, preferably in an appropriate organic solvent. The ratio of the compound having an epoxy group and a polymerizable group containing a C=C double bond used in the reaction is preferably 0.01 to 0.9 per mole of carboxyl groups contained in the polymer having a carboxyl group. mole, more preferably 0.05~0.8 mole, more preferably 0.1~0.7 mole.

As the organic catalyst that can be used here, a compound known as a so-called hardening accelerator that accelerates the reaction between an organic base or an epoxy compound and a carboxyl group can be used.

Examples of the above-mentioned organic base include 1st and 2nd-level organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; such as triethylamine, tri-n-propylamine, and tri-n-butylamine. , pyridine, 4-dimethylaminopyridine, 3-level organic amines of diazabicycloundecene; such as 4-level organic amines of tetramethylammonium hydroxide, etc. Among these organic bases, preferred are tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine; such as tetramethylammonium hydroxide Class 4 organic amines.

Examples of the above-mentioned hardening accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-shen(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; such as 2-methane 2-n-heptyl imidazole, 2-n-undecyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-( 2-cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl -4-Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di(hydroxymethyl)imidazole, 1-(2-cyanoethyl) )-2-phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium Trimellitic acid salt, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium Trimellitic acid salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-(2 '-n-Undecyl imidazolyl)ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl -s-triazine, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2,4-diamino-6-[2' -Imidazole compound of isocyanuric acid adduct of -methylimidazolyl-(1')]ethyl-s-triazine; such as diphenylphosphine, triphenylphosphine, organophosphorus of triphenyl phosphite compound;

Such as benzyl triphenyl phosphonium chloride, tetrakis-n-butyl phosphonium bromide, methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, n-butyl triphenyl phosphonium bromide, tetrakis Phenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetrakis-n-butylphosphonium o,o-diethylphosphodisulfonate, tetrakis-n- Butylphosphonium benzotriazole salt, tetrakis-n-butylphosphonium tetrafluoroborate, tetrakis-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate and the 4th grade phosphonium salt; such as Diazabicyclones of 1,8-diazabicyclo[5.4.0]undecene-7 or its organic acid salts; such as zinc octoate, tin octoate, and organic metal compounds of aluminum acetyl acetone complexes; such as Tetraethylammonium bromide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium chloride, tetraethylammonium chloride, 4th grade ammonium salt; such as boron trifluoride, triphenyl borate Boron compounds; metal halide compounds such as zinc chloride and tin (IV) chloride; amine addition accelerators such as dicyandiamine or adducts of amines and epoxy resins, etc. High melting point dispersion type latent hardening accelerators Agent; microcapsule type latent hardening accelerator obtained by coating the surface of the aforementioned imidazole compound, organophosphorus compound or fourth-grade phosphonium salt hardening accelerator with a polymer; amine salt type latent hardening accelerator; Lewis Potential hardening accelerators such as high-temperature dissociation type thermal cationic polymerization type latent hardening accelerators such as acid salts and bronzite salts. Among these, quaternary ammonium salts such as tetraethylammonium bromide, tetraethylammonium bromide, tetraethylammonium chloride, and tetraethylammonium chloride are preferred.

The usage ratio of the catalyst is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and still more preferably 0.1 to 100 parts by mass relative to 100 parts by mass of the polymer having an epoxy group or the polymer having a carboxyl group. 20 parts by mass.

Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. Among these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferred from the viewpoint of the solubility of the raw materials and products and the ease of purification of the products. The solvent is used in an amount such that the solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1 mass % or more, more preferably 5 to 50 mass %.

The reaction temperature is preferably 0 to 200°C, more preferably 50 to 150°C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

＜Production method of (A) component 3＞ Method 3 for producing component (A) is a method of reacting a cinnamic acid derivative and the aforementioned compound having a carboxyl group and a polymerizable group containing a C=C double bond with a polymer having an epoxy group in the side chain.

The polymer with an epoxy group in the side chain can be, for example, the polymer of the aforementioned monomer with an epoxy group, or the aforementioned monomer with an epoxy group, and the aforementioned monomer with a non-reactive functional group. body copolymer.

The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group is preferably 30 mass% or more, more preferably 50 mass% or more.

The synthesis of the polymer having an epoxy group can preferably be carried out by a known free radical polymerization method in a solvent and in the presence of an appropriate polymerization initiator.

Commercially available polymers having epoxy groups in their side chains can also be used. Examples of such commercially available products include EHPE3150, EHPE3150CE (above, manufactured by Daicel Co., Ltd.), UG-4010, UG-4035, UG-4040, UG-4070 (above, ARUFON series manufactured by Toa Gosei Co., Ltd.), ECN- 1299 (manufactured by Asahi Kasei Co., Ltd.), DEN431, DEN438 (above, manufactured by Dow Chemical Co., Ltd.), jER-152 (manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON N-660, N-665, N-670, N-673 , N-695, N-740, N-770, N-775 (above, manufactured by DIC Co., Ltd.), EOCN-1020, EOCN-102S, EOCN-104S (above, manufactured by Nippon Kayaku Co., Ltd.), etc.

Examples of cinnamic acid derivatives having a carboxyl group include the following formulas (1-1) to (1-5) (In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, etc.). Furthermore, as the cinnamic acid derivative having a carboxyl group, a compound in which X ¹ is a hydrogen atom in the monomer represented by the above formula [3] is also suitably used.

The above-mentioned cinnamic acid derivatives can be synthesized by appropriately combining prescribed methods of organic chemistry.

Here, the compound (monomer) having a carboxyl group and a polymerizable group containing a C=C double bond is preferably one having a spacer group between the group having a C=C double bond and the carboxyl group, as mentioned above.

The method of reacting a cinnamic acid derivative and the aforementioned compound having a carboxyl group and a polymerizable group containing a C=C double bond with a polymer having an epoxy group in the side chain is as described above. At this time, the cinnamic acid derivative and the aforementioned compound having a carboxyl group and a polymerizable group containing a C=C double bond may be reacted together with the polymer having an epoxy group in the side chain, or they may be reacted separately.

In the polymer of component (A), the proportion of structural units having a polymerizable group containing a C=C double bond is preferably 5 mol% relative to 100 mol% of all structural units of the polymer. More than 10 mol%, preferably more than 10 mol%. When the total amount is less than 5 mol%, the adhesiveness with the liquid crystal layer may become insufficient. Here, when the polymer of component (A) contains two or more structural units having a polymerizable group containing a C=C double bond, the proportion of the structural units having a polymerizable group containing a C=C double bond is, It means the number of moles of the total structural units of the polymer per 100 moles (the number of moles of the structural unit having a polymerizable group containing a C=C double bond) × (the number of polymers containing a C=C double bond contained in the structural unit number of sexual bases).

In this way, a solution containing a polymer having a photoalignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond as the component (A) can be obtained. The solution can be directly used for the preparation of a liquid crystal alignment agent, the polymer contained in the solution can be isolated and used for the preparation of a liquid crystal alignment agent, or the isolated polymer can be purified and used for the preparation of a liquid crystal alignment agent.

In addition, the solution of the specific copolymer obtained as above is put into diethyl ether or water and stirred to perform redrecipitation, and the generated precipitate is filtered/washed, and then subjected to normal pressure or It can be dried under reduced pressure at room temperature or heated to become the powder of a specific copolymer. By such an operation, the polymerization initiator or unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If it is not possible to purify sufficiently with one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

In the cured film-forming composition of the present invention, the powder of the above-mentioned specific copolymer can be used directly as the component (A), or the powder can be redissolved in a solvent described below and used as a solution.

Furthermore, in this embodiment, the acrylic copolymer of component (A) may be a mixture of a plurality of specific copolymers.

As described above, in the present invention, a specific copolymer of high molecular weight can be used as the component (A). In addition, component (A) may be a mixture of one or more specific copolymers.

[(B)Component] The cured film forming composition of the present invention contains a cross-linking agent as component (B). More specifically, the component (B) is a cross-linking agent that reacts with the component (A) and (C) mentioned above. The component (B) is bonded to the thermally crosslinkable group (especially hydroxyl group) of the polymer of the component (A) and the hydroxyl group contained in the component (C). In addition, the cured film forming composition of this embodiment can form an alignment material with high photoreaction efficiency as a cured film.

Examples of the crosslinking agent of the component (B) include epoxy compounds, methylol compounds, isocyanate compounds, and the like, and a methylol compound is preferred. Among them, the cross-linking agent of component (B) is particularly preferably a compound having two or more groups that form cross-links with the thermally cross-linkable functional group of component (A). For example, a compound having two or more groups is preferred. hydroxymethyl or alkoxymethyl cross-linking agent. Examples of compounds having such groups include methylol compounds such as alkoxymethylated acetylene urea, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of the hydroxymethyl compound include alkoxymethylated acetylene urea, alkoxymethylated benzoguanamine, alkoxymethylated melamine, and tetrakis(alkoxymethyl)bisphenol. And compounds such as tetra(hydroxymethyl)bisphenol.

Specific examples of alkoxymethylated acetylene urea include 1,3,4,6-quaternary (methoxymethyl) acetylene urea and 1,3,4,6-quaternary (butoxymethyl) Acetylene urea, 1,3,4,6-(hydroxymethyl)acetylene urea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-(butoxymethyl)urea, 1,1,3,3-Methoxymethylurea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methyl) Oxymethyl)-4,5-dimethoxy-2-imidazolinone, etc. Examples of commercially available products include compounds such as acetylene urea compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., and methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd. urea/formaldehyde resin (high condensation type, trade name: BECKAMINE (registered trademark) J-300S, same as P-955, same as N), etc.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Examples of commercially available products include Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered trademark)) BX-4000, BX-37, and BL -60, same as BX-55H), etc.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine. Examples of commercially available products include methoxymethyl melamine compounds (trade names: Cymel (registered trademark) 300, Cymel (registered trademark) 300, Cymel 303, Cymel 350) manufactured by Mitsui Cytec Co., Ltd., and butoxymethyl melamine compounds (trade names). Name: Mycoat (registered trademark) 506, same as 508), methoxymethyl melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered trademark) MW-30, same as MW-22, same as MW-11 , same as MW-100LM, same as MS-001, same as MX-002, same as MX-730, same as MX-750, same as MX-035), butoxymethyl melamine compound (trade name: NIKALAC (registered trademark) MX -45, same as MX-410, same as MX-302), etc.

Examples of tetrakis(alkoxymethyl)bisphenol and tetrakis(hydroxymethyl)bisphenol include tetrakis(alkoxymethyl)bisphenol A, tetrakis(hydroxymethyl)bisphenol A, and the like.

In addition, the cross-linking agent of component (B) may be a melamine compound, a urea compound, an acetylene urea compound and a benzoguanamine compound in which the hydrogen atom of the amine group is substituted by a hydroxymethyl group or an alkoxymethyl group. The compound obtained. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in US Patent No. 6323310 can be cited. Examples of commercially available products of the aforementioned melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and examples of commercially available products of the aforementioned benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (controlled by Mitsui Cytec Co., Ltd.), etc.

Furthermore, as the cross-linking agent of component (B), N-hydroxymethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide, N -Polymers made from acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl (i.e., hydroxymethyl) or alkoxymethyl groups, such as butoxymethylmethacrylamide.

Examples of such polymers include poly(N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, and N-hydroxymethylmethacrylamide and Copolymers of methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethacrylamide and benzyl methacrylate and methacrylate Copolymer of 2-hydroxypropyl acrylate, etc.

Furthermore, as such a polymer, a polymer having an N-alkoxymethyl group and a polymerizable group containing a C=C double bond can also be used.

Examples of the polymerizable group containing a C=C double bond include an acryl group, a methacryloyl group, a vinyl group, an allyl group, a maleimide group, and the like.

The method for obtaining a polymer having a polymerizable group containing a C=C double bond is not particularly limited. For example, an acrylic polymer having a specific functional group is produced in advance by a polymerization method such as radical polymerization. Next, by reacting the specific functional group with a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound), a polymerizable group containing a C=C double bond can be introduced into the polymer of component (B).

Here, the specific functional group refers to a functional group such as a carboxyl group, a glycidyl group, a hydroxyl group, an amine group having an active hydrogen, a phenolic hydroxyl group, an isocyanate group, or a plurality of functional groups selected from these groups. By polymerizing monomers having these groups, acrylic polymers having specific functional groups can be obtained.

Examples of monomers having carboxyl groups include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl) phthalate, and mono-(2-(methacryloxy)ethyl). Oxy)ethyl) phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide and N-(carboxyphenyl)acrylamide wait.

Examples of monomers having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1, 2-epoxy-5-hexene and 1,7-octadiene monoepoxide, etc.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and methyl 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloxy)ethyl ester, caprolactone 2-(methacryloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether Methacrylate, 5-acryloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone and 5-methacryloxy-6-hydroxynorbornene-2-carboxylic acid Acid-6-lactone, etc.

Examples of the monomer having an amino group include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

Monomers with phenolic hydroxyl groups include, for example, hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleamide. Amines etc.

Examples of the monomer having an isocyanate group include acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethylxylene isocyanate, and the like.

In the above reaction, the preferred combinations of specific functional groups and functional groups related to the reaction possessed by the specific compound are carboxyl and epoxy groups, hydroxyl and isocyanate groups, phenolic hydroxyl and epoxy groups, carboxyl and isocyanate groups, Amino group and isocyanate group, or hydroxyl group and acid chloride, etc. Furthermore, a more preferred combination is carboxyl and glycidyl methacrylate, or hydroxyl and isocyanate ethyl methacrylate.

The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, still more preferably 3,000 to 50,000.

These cross-linking agents can be used alone or in combination of two or more.

The content of the cross-linking agent of component (B) in the cured film forming composition of the present invention is preferably based on 100 parts by mass of the total amount of the polymer of component (A) and the cross-linking catalyst of component (C). The amount is 5 parts by mass to 500 parts by mass, and more preferably 10 parts by mass to 400 parts by mass. If the content of the cross-linking agent is too small, the solvent resistance of the cured film obtained from the cured film-forming composition may decrease, and the liquid crystal alignment may decrease. On the other hand, when the content is too large, liquid crystal alignment and storage stability may be reduced.

[(C)Component] The cured film-forming composition that forms the cured film on the surface of the optical film of the present invention may further contain a crosslinking catalyst of the component (C) in addition to the above-mentioned components (A) and (B). Examples of the cross-linking catalyst of component (C) include acid or thermal acid generator. This component (C) is effective in promoting a thermosetting reaction when a cured film is formed using a cured film-forming composition that forms a cured film on the surface of the optical film of the present invention.

When an acid or thermal acid generator is used as component (C), component (C) only needs to be a compound containing a sulfonic acid group, hydrochloric acid or its salt, or a compound that generates acid by thermal decomposition during pre-baking or post-baking, that is, There are no special restrictions on compounds that thermally decompose at temperatures between 80°C and 250°C to produce acids.

Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, and trifluoromethanesulfonate. Acid, p-phenol sulfonic acid, 2-naphthalene sulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H,2H,2H-Perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, etc. Sulfonic acid or its hydrate or salt, etc.

Examples of compounds that generate acids due to heat include bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, and p-toluenesulfonate. Nitrobenzyl ester, o-nitrobenzyl tosylate, 1,2,3-phenylenesulfonate (methylsulfonate), p-pyridinium tosylate, p-morpholinium tosylate Salt, p-ethyl toluenesulfonate, p-propyl toluenesulfonate, p-butyl toluenesulfonate, p-isobutyl toluenesulfonate, p-methyl toluenesulfonate, p-phenyl toluenesulfonate Ester, p-cyanomethyl toluenesulfonate, p-2,2,2-trifluoroethyl toluenesulfonate, p-hydroxybutyl toluenesulfonate, N-ethyl-4-toluenesulfonamide , and compounds represented by the following formulas [TAG-1] to formulas [TAG-41], etc.

The content of component (C) in the cured film forming composition according to the embodiment of the present invention is 0.01 to 20 parts by mass, preferably 0.01 part by mass relative to 100 parts by mass of the polymer of component (A). ~10 parts by mass, more preferably 0.05 parts by mass ~ 8 parts by mass, and more preferably 0.1 parts by mass ~ 6 parts by mass. By setting the content of component (C) to 0.01 parts by mass or more, sufficient thermal curability and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted. Moreover, by being 20 parts by mass or less, the storage stability of the cured film forming composition can be made good.

[(D)Component] The composition of the present invention may further contain a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a amide group, an amine group, and an alkoxysilyl group as the component (D).

Examples of the polymer of component (D) include acrylic polymer, urethane-modified acrylic polymer, polyamide, polyimide, polyvinyl alcohol, polyester, polyester-polycarboxylic acid, polyamide Ether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkylenimine, polyallylamine, cellulose (cellulose or its derivatives), phenolic novolac resin Polymers with linear or branched structures, cyclic polymers such as cyclodextrins, etc.

Among them, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylate, methacrylate, styrene, etc. can be used as the acrylic polymer. As the synthesis method, a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having a amide group, and a monomer having an amine group selected from the group consisting of the above-mentioned components (A) and (B) are exemplified. At least one monomer of the group consisting of a monomer and a monomer having an alkoxysilyl group, and other monomers as desired, as described in the chapters of the above-mentioned (A) component and (B) component. Methods The method of (co)polymerization is simple.

The weight average molecular weight of the acrylic polymer as an example of component (D) is preferably 3,000 to 200,000, more preferably 4,000 to 150,000, still more preferably 5,000 to 100,000.

Preferable examples of polyether polyols as component (D) include propylene oxide or polyethylene added to polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, sorbitol, and other polyols. Glycol, polypropylene glycol, etc. Specific examples of polyether polyols include Adeka Polyether P series, G series, EDP series, BPX series, FC series, CM series manufactured by ADEKA Co., Ltd., Uniox (registered trademark) HC-40, HC manufactured by NOF Co., Ltd. -60, ST-30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA- 700, DB-400, Nonion (registered trademark) LT-221, ST-221, OT-221, etc.

Preferable examples of the polyester polyol of component (D) include glycols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, and polypropylene glycol, and adipic acid, sebacic acid, isophthalic acid, etc. Formic acid and other polycarboxylic acid reactants. Specific examples of the polyester polyol include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, manufactured by DIC Co., Ltd. OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD- X-2523, OD-X-2555, OD-X-2560, Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, manufactured by Kuraray Co., Ltd. F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc.

A preferred example of polycaprolactone polyol as component (D) is one in which ε-caprolactone is ring-opening polymerized using a polyol such as trimethylolpropane or ethylene glycol as a initiator. Specific examples of polycaprolactone polyol include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC Co., Ltd., Placcel (registered trademark) 205 manufactured by Daicel Chemical Co., Ltd. L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc.

A preferred example of the polycarbonate polyol of the component (D) is one made by reacting a polyol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, or the like. Specific examples of polycarbonate polyols include Placcel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Co., Ltd., C-590, C-1050, C-2050, C-2090 manufactured by Kuraray Co., Ltd. C-3090 etc.

Preferable examples of cellulose as the component (D) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl methyl cellulose. Hydroxyalkyl alkyl celluloses such as hydroxyethyl ethyl cellulose and cellulose, etc. are preferably hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.

Preferable examples of cyclodextrins as the component (D) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; methyl-α-cyclodextrin, methyl-β - Methylated cyclodextrins such as cyclodextrin and methyl-γ-cyclodextrin; hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin Essence, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3- Hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, 2,3-dihydroxypropyl-γ -Hydroxyalkyl cyclodextrin, etc. of cyclodextrin, etc.

(D) A preferred example of the urethane-modified acrylic polymer of the component, commercially available products include Acrit (registered trademark) 8UA-017, 8UA-239, 8UA-239H manufactured by Daesung Fine Chemical Co., Ltd. 8UA-140, 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, 8UA-366, etc.

A preferred example of the phenol novolac resin as the component (D) includes, for example, a phenol-formaldehyde polycondensate.

In the composition of the present invention, the polymer of component (D) can be used in the form of powder or in the form of a solution obtained by redissolving the purified powder in a solvent described below.

Furthermore, in the composition of the present invention, component (D) may be a mixture of plural types of polymers exemplified as component (D).

The content of component (D) in the cured film forming composition of the present invention is 5 to 500 parts by mass based on 100 parts by mass of component (A).

[(E) Component] The composition of the present invention may further contain a low molecular weight photo-alignment component as the (E) component. By containing low-molecular photo-alignment components, the amount of photo-alignment groups on the surface of the alignment film is increased, thereby improving the alignment sensitivity. Such low molecular weight photoalignment components can be listed among the monomer represented by formula [3], the monomer represented by formula [4], and the monomer represented by formula [3] exemplified in the section (A) component of this specification. Compounds ⁱⁿ which ^the base Cinnamic acid derivatives.

Furthermore, in the composition of the present invention, component (E) may be a mixture of a plurality of compounds exemplified as component (E).

When the cured film forming composition of the present invention contains component (E), the content is 5 to 500 parts by mass based on 100 parts by mass of the polymer of component (A).

[Other additives] The cured film forming composition according to the embodiment of the present invention may contain other additives as long as the effects of the present invention are not impaired. As other additives, a sensitizer may be included, for example. The sensitizer is effective in promoting the photoreaction when forming a cured film on the surface of the optical film of the present invention.

Examples of the sensitizer include derivatives of benzophenone, anthracene, anthraquinone, thioxanthone, and nitrophenyl compounds. Particularly preferred among these are N,N-diethylamine benzophenone, which is a derivative of benzophenone, and 2-nitrobenzene, 2-nitrobenzone, 5-nitrophenyl compounds, which are nitrophenyl compounds. -Nitroacenaphthylene, 4-nitrobephenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, 5-nitroindole.

These sensitizers are not particularly limited to those mentioned above. These compounds may be used alone or in combination of two or more.

In the embodiment of the present invention, the usage ratio of the sensitizer is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass relative to 100 parts by mass of component (A). If the ratio is too small, the effect as a sensitizer may not be fully obtained. If the ratio is too large, the transmittance of the cured film formed may be reduced or the coating film may be rough.

In addition, the cured film-forming composition according to the embodiment of the present invention may contain silane coupling agents, surfactants, rheology regulators, pigments, dyes, and storage stabilizers as other additives as long as the effects of the present invention are not impaired. , defoaming agents, antioxidants, etc.

[Solvent] The cured film-forming composition according to the embodiment of the present invention is often used in a solution state dissolved in a solvent. The solvent used at this time is one that can dissolve component (A), (B) and (C), as well as component (D), (E) and/or other additives as desired, as long as it has such dissolving ability. The type and structure of the solvent are not particularly limited.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methylcellulosulfonate acetate, ethylcellulosulfonate acetate, and diethylene glycol monomethyl ether. ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene , xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2 -Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyethyl acetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, acetic acid Butyl ester, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate, isopropyl alcohol, N,N-dimethylformamide, N,N-dimethylacetamide, and N -Methyl-2-pyrrolidone, etc.

These solvents can be used alone or in combination of two or more. Among these solvents, due to their good film-forming properties and high safety, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, cyclohexanone, 2-heptanone, and propylene glycol are more preferred. Propyl ether, propylene glycol propyl ether acetate, ethyl acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropane Ethyl acid ester and methyl 3-ethoxypropionate.

＜Preparation of cured film forming composition＞ The cured film-forming composition of the present invention is a thermosetting cured film-forming composition having photoalignment properties. The cured film forming composition of the present invention contains, as mentioned above, a polymer having a photo-alignment group and a hydroxyl group as the component (A), a polymerizable group containing a C=C double bond, and a cross-linking agent as the component (B). and the cross-linking catalyst of component (C). If necessary, the polymer containing (D) component has at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a amide group, an amino group, and an alkoxysilyl group. As long as the effect of the present invention is not impaired, other additives may be included, and further, a solvent may be included.

Preferable examples of the cured film forming composition of this embodiment are as follows. [1]: A polymer containing a photoalignable group, a hydroxyl group, and a polymerizable group containing a C=C double bond as the component (A), 1 part by mass based on 100 parts by mass of the polymer as the component (A) ~500 parts by mass, preferably 5 parts by mass to 500 parts by mass of the cross-linking agent of component (B), and 0.01 parts by mass to 20 parts by mass relative to 100 parts by mass of the polymer of component (A) (C) A cured film-forming composition of a cross-linking catalyst of the component.

[2]: A polymer containing a photoalignable group, a hydroxyl group, and a polymerizable group containing a C=C double bond as the component (A), 1 part by mass based on 100 parts by mass of the polymer as the component (A) ~500 parts by mass, preferably 5 parts by mass to 500 parts by mass of the cross-linking agent of component (B), and 0.01 parts by mass to 20 parts by mass relative to 100 parts by mass of the polymer of component (A) The cross-linking catalyst and solvent of the component (C), and further, 5 to 500 parts by mass of the component (D) having a hydroxyl group and a carboxyl group selected from 100 parts by mass of the polymer of the component (A). , a cured film-forming composition of a polymer and a solvent containing at least one type of group consisting of a amide group, an amine group and an alkoxysilane group.

The blending ratio, preparation method, etc. when using the cured film forming composition of this embodiment as a solution are described in detail below.

The proportion of solid components in the cured film forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent. It is 1 mass% to 80 mass%, preferably 2 mass% to 60 mass%, and more preferably It is 3 mass%~40 mass%. Here, the solid content refers to all the components of the cured film-forming composition excluding the solvent.

The preparation method of the cured film forming composition of the present invention is not particularly limited. Preparation methods include, for example, mixing component (B), component (C), component (D), component (E) and/or other additives in a specific ratio into a solution of component (A) dissolved in a solvent to form a uniform mixture. solution method, or a method in which other additives are further added and mixed as needed at appropriate stages of the preparation method.

In the preparation of the cured film-forming composition of the present invention, a solution of a specific copolymer obtained by polymerization in a solvent can be directly used. At this time, for example, in the solution of the polymer (acrylic polymer) prepared with component (A), component (B), component (C), and further component (D), component (E) and/or other additives are added, become a homogeneous solution. At this time, additional solvent may be added for the purpose of adjusting the concentration. At this time, the solvent used in the preparation process of component (A) and the solvent used in adjusting the concentration of the cured film forming composition may be the same or different.

In addition, the prepared solution of the cured film-forming composition is preferably filtered using a filter with a pore size of about 0.2 μm before use.

As described above, the cured film-forming composition of the present invention contains a polymer selected from the group consisting of (A) component having a photoalignment group, a hydroxyl group, and a polymerizable group containing a C=C double bond. It consists of at least one cross-linking agent of component (B) and a cross-linking catalyst of component (C).

Therefore, the inside of the cured film formed from the cured film-forming composition of the present invention becomes hydrophilic due to the properties of component (A) to stabilize the film structure. The photo-alignment group of component (A) in the cured film and the polymerizable group containing C=C double bonds are mostly present near the surface of the cured film. More specifically, the polymer of component (A) has a structure in which the hydrophilic hydroxyl group faces the inner side of the cured film, the hydrophobic photoreactive portion and the polymerizable group containing the C=C double bond face the surface side. Most of them are found near the surface of the hardened film. As a result, the cured film of the present invention has a structure in which the proportion of the photoreactive group and the polymerizable group containing the C=C double bond of component (A) present near the surface is increased. In addition, when used as an alignment material, the cured film of the present invention can improve the efficiency of photoreaction for photoalignment and can have excellent alignment sensitivity. Furthermore, the alignment material is suitable for forming patterned retardation materials, and the patterned retardation materials produced using the alignment material can have excellent pattern formability.

Moreover, the cured film forming composition of this invention contains the crosslinking agent of (B) component as mentioned above. Therefore, inside the cured film obtained from the cured film-forming composition of the present invention, before the photoreaction caused by the photoalignment group of the polymer of the component (A), it is possible to react with the heat of the component (B). Carry out cross-linking reaction. As a result, when used as an alignment material, the resistance to the polymerizable liquid crystal or its solvent coated thereon can be improved.

Furthermore, when the cured film obtained from the cured film-forming composition of the present invention is used as an alignment material, the polymerizable group containing a C=C double bond in the polymer of component (A) strengthens the structure formed thereon. It functions through the adhesion between layers of hardened polymeric liquid crystal.

＜Cure film, alignment material and phase difference material＞ The solution of the cured film forming composition of this embodiment is applied to a substrate (such as a silicon/silica-coated substrate, a silicon nitride substrate, a substrate coated with metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate) etc.) or films (such as triacetyl cellulose (TAC) films, cyclic olefin polymer films, polyethylene terephthalate films, acrylic films, resin films, etc.), etc., by rod coating, rotating Coating, flow coating, roll coating, slit coating, slit spin coating, inkjet coating, printing, etc. can be applied to form a coating film. After that, it can be heated with a hot plate or oven. Dry to form a hardened film.

The conditions for heating and drying are as long as the hardening reaction proceeds to the extent that the components of the alignment material formed by the cured film will not dissolve in the polymerizable liquid crystal solution coated on it. For example, the temperature range is from 60°C to 200°C. , the heating temperature and heating time should be appropriately selected within the range of 0.4 minutes to 60 minutes. The heating temperature and heating time are preferably 70°C to 160°C and 0.5 minutes to 10 minutes.

The film thickness of the cured film formed using the curable composition of this embodiment is, for example, 0.05 μm to 5 μm, and can be appropriately selected in consideration of the step difference or optical and electrical properties of the substrate used.

The cured film formed in this way can function as an alignment material, that is, a member containing a liquid crystalline compound such as polymerizable liquid crystal, by irradiating it with polarized UV light.

The polarized UV irradiation method usually uses ultraviolet light to visible light with a wavelength of 150nm to 450nm, and is carried out by irradiating linearly polarized light from a vertical or oblique direction at room temperature or under heating.

An alignment material formed using a cured film formed of the cured film-forming composition of the present invention has solvent resistance and heat resistance. Therefore, after coating a retardation material composed of a polymerizable liquid crystal solution on the alignment material, it is Heating to the phase transition temperature of the liquid crystal causes the phase difference material to become a liquid crystal state and aligns the material on the alignment material. Then, the retardation material in the desired alignment state can be directly hardened to form a retardation material having a layer having optical anisotropy.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the liquid crystal monomer are used. When the substrate on which the alignment material is formed is a thin film, the thin film containing the retardation material of this embodiment is useful as a retardation film. The retardation material that forms such a retardation material becomes a liquid crystal state. If the alignment material adopts an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, mixed alignment, etc., each can be configured according to the necessary phase difference characteristics. used separately.

In addition, when manufacturing a patterned retardation material used in a 3D display, the cured film formed from the cured film-forming composition of the present invention by the above-mentioned method is used to pass a line and space pattern based on a specific reference. Mask, for example, perform polarized UV exposure in the direction of +45 degrees. Then, remove the mask and perform polarized UV exposure in the direction of -45 degrees to form one of two types of liquid crystal alignment areas with different alignment control directions of liquid crystals. Alignment materials. Thereafter, a retardation material composed of a polymerizable liquid crystal solution is applied, and then the retardation material is brought into a liquid crystal state by heating to the phase transition temperature of the liquid crystal. The polymerizable liquid crystal that becomes a liquid crystal state is aligned on an alignment material in which two types of liquid crystal alignment areas are formed, forming an alignment state corresponding to each liquid crystal alignment area. Then, the retardation material that achieves such an alignment state can be directly hardened to fix the above-mentioned alignment state, thereby obtaining a patterned retardation material in which a plurality of two types of retardation regions with different retardation characteristics are regularly arranged.

Furthermore, an alignment material formed using a cured film formed of the cured film-forming composition of the present invention can also be utilized as a liquid crystal alignment film for a liquid crystal display element. For example, two substrates having the alignment material of the present invention formed as described above can be used. After the alignment materials on the two substrates face each other through a spacer, liquid crystal can be injected between the substrates. Manufacture of liquid crystal display elements with aligned liquid crystals. Therefore, the cured film-forming composition of this embodiment can be suitably used for manufacturing various retardation materials (retardation films), liquid crystal display elements, and the like. [Example]

Hereinafter, examples of the present invention are enumerated to illustrate the present invention in detail, but the present invention is not limited to these examples.

[Abbreviations used in the examples] The meanings of the abbreviations used in the following examples are as follows. <Raw materials> GMA: Glycidyl methacrylate AIBN: α,α'-azobisisobutyronitrile BMAA: N-butoxymethacrylamide CIN1: CIN2:

P-2: EHPE3150 (manufactured by Daicel Co., Ltd., epoxy equivalent 180g/eq)

A-1: Aronix M-5300 (manufactured by Toa Gosei Co., Ltd.)

A-2: Aronix M-5400 (manufactured by Toa Gosei Co., Ltd.)

A-3: 2-propenyloxyethyl succinate

<Component B> HMM: Melamine cross-linking agent represented by the following structural formula [Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.)]

＜C component＞ PTSA: p-toluenesulfonic acid･monohydrate

<D component> PEPO: Polyester polyol polymer (adipic acid/diethylene glycol copolymer having the following structural units. Molecular weight 4,800) (In the above formula, R represents an alkylene group)

＜Solvent＞ PM: propylene glycol monomethyl ether EA: Ethyl acetate

＜Measurement of molecular weight of polymer＞ The molecular weight of the acrylic (co)polymer in the polymerization examples was determined using a normal temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Shodex Corporation, a column (KD-803, manufactured by Shodex Corporation). KD-805) was measured as follows. In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene conversion values. Tube string temperature: 40℃ Eluate: Tetrahydrofuran Flow rate: 1.0mL/min Standard sample for calibration line preparation: Standard polystyrene manufactured by Showa Denko Co., Ltd. (molecular weight: approximately 197,000, 55,100, 12,800, 3,950, 1,260, 580).

＜Synthesis of component A＞ ＜Synthesis example 1＞ Dissolve 15.0g of GMA and 0.8g of AIBN as a polymerization catalyst in 63.0g of tetrahydrofuran, and react under heating and reflux for 20 hours to obtain an acrylic acid polymer solution. The acrylic polymer solution was slowly dropped into 500.0 g of diethyl ether to precipitate a solid. The acrylic polymer (P-1) was obtained by filtration and drying under reduced pressure. The obtained acrylic polymer had an Mn of 6,500 and a Mw of 11,000.

＜Synthesis example 2＞ 10.0 g of the acrylic polymer (P-1) having an epoxy group obtained in Synthesis Example 1, 8.4 g of CIN1, 0.8 g of acrylic acid, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, and 0.1 g of ethyltriphenylphosphonium bromide as a polymerization inhibitor. 0.4 g of dibutylhydroxytoluene as an agent was dissolved in 46.1 g of PM, and the mixture was reacted at 80°C for 20 hours to obtain a solution containing 30% by mass of acrylic polymer (PA-1). The epoxy valency of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

＜Synthesis Examples 3~10＞ In addition to making the types and blending amounts of the polymer having an epoxy group (acrylic polymer), the compound imparting a photo-alignment group, and the compound imparting a polymerizable double bond-containing group as shown in Table 1 below, The same operation was performed in Synthesis Example 2 to obtain a solution containing 30% by mass of polymers (PA-2) to (PA-9). Furthermore, empty columns in Table 1 indicate that the component is not blended.

＜Synthesis of component B＞ ＜Synthesis Example 11＞ Dissolve 100.0g of BMAA and 4.2g of AIBN as a polymerization catalyst in 193.5g of PM, and react at 90°C for 20 hours to obtain an acrylic polymer solution. The obtained acrylic polymer had Mn of 2,700 and Mw of 3,900. The acrylic polymer solution was slowly dropped into 2000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain polymer (PB-1).

＜Preparation of polymerizable liquid crystal solution＞ 29.0g of polymerizable liquid crystal LC242 (manufactured by BASF Corporation), 0.9g of Irgacure 907 (manufactured by BASF Corporation) as a polymerization initiator, 0.2g of BYK-361N (manufactured by BYK Corporation) as a leveling agent, and methyl group as a solvent were added isobutyl ketone to obtain a polymerizable liquid crystal solution (RM-1) with a solid content concentration of 30% by mass.

<Example 1> The solution containing 30% by mass of the acrylic polymer (PA-1) obtained in the above synthesis example 2 as the component (A) was mixed in an amount equivalent to 100 parts by mass in terms of the acrylic polymer (PA-1), as 30 parts by mass of HMM as component (B) and 3 parts by mass of PTSA as component (C) were added to PM and EA to prepare a solvent composition of PM:EA=100:30 (mass ratio) and a solid content concentration of 5.0 mass. % of the cured film (alignment material) forms the composition (A-1).

<Examples 2 to 12 and Comparative Examples 1 to 2> Except that the types and amounts of each component were as described in Table 2, the same procedure was carried out as in Example 1, and cured film (alignment material) forming compositions A-2 to A-15 were respectively prepared. Furthermore, empty columns in Table 2 indicate that the component is not blended.

<Examples 13 to 24 and Comparative Examples 3 to 4> [Evaluation of Alignment] Each cured film (alignment material) of Examples 1 to 12 and Comparative Examples 1 to 2 was formed into a composition, using a bar coater with Wet The film thickness is 4 μm and is coated on the TAC film. Heat and dry in a thermal cycle oven at a temperature of 110° C. for 60 seconds to form a cured film on the film. Each cured film was vertically irradiated with linearly polarized light of 313 nm at an exposure dose of 10 mJ/cm ² to form an alignment material. The polymerizable liquid crystal solution (RM-1) was coated on the alignment material on the film using a rod coater with a Wet film thickness of 6 μm. The coating film was dried on a hot plate at a temperature of 90° C. for 60 seconds, and then exposed to 300 mJ/cm ² to produce a phase difference material. The retardation material on the produced film was sandwiched between a pair of polarizing plates, and the performance of the retardation characteristics of the retardation material was observed. Those that showed the retardation without defects were marked as ○, and those that did not show the retardation were marked as ×. in the "Orientation" column. The evaluation results are collectively shown in Table 3 described below.

[Evaluation of Adhesion] Each cured film (alignment material) forming composition of Examples 1 to 12 and Comparative Examples 1 to 2 was applied on the TAC film with a Wet film thickness of 4 μm using a bar coater. Heat and dry in a thermal cycle oven at a temperature of 110° C. for 60 seconds to form a cured film on the film. Each cured film was vertically irradiated with linearly polarized light of 313 nm at an exposure dose of 10 mJ/cm ² to form an alignment material. The polymerizable liquid crystal solution (RM-1) was coated on the alignment material on the film using a rod coater with a Wet film thickness of 6 μm. The coating film was dried on a hot plate at a temperature of 90° C. for 60 seconds, and then exposed to 300 mJ/cm ² to produce a phase difference material. In this phase difference material, cut out a 5×5 square grid with a cutting knife at intervals of 1 mm in length and width. Use Scotch tape on this incision to perform a Cellophane tape peel test. The evaluation results are recorded as "adhesion", and the number of squares remaining without peeling out of the 25 squares is recorded. For example, if it is 25/25, it means that all the squares are not peeled off but remain, and the adhesion is high. The evaluation results are collectively shown in Table 3 described below.

As shown in Table 3, the phase difference materials obtained in Examples 13 to 24 showed good alignment and high adhesion.

On the other hand, the retardation material obtained in Comparative Example 3 showed good alignment, but sufficient adhesion was not obtained. In addition, the retardation material obtained in Comparative Example 4 had insufficient alignment and adhesion properties. [Industrial availability]

The cured film formed from the cured film-forming composition of the present invention is very useful as an alignment material for a liquid crystal alignment film used to form a liquid crystal display element or an optically anisotropic film provided inside or outside a liquid crystal display element. In particular, the cured film-forming composition of the present invention is suitable as a material for forming a cured film of a patterned retardation material used in a 3D display. Furthermore, the cured film-forming composition of the present invention is also suitable as a material for forming cured films such as protective films, flat films, and insulating films in various displays such as thin film transistor (TFT) liquid crystal display elements or organic EL elements. , especially materials that form interlayer insulating films for TFT-type liquid crystal display elements, protective films for color filters, or insulating films for organic EL elements.

Claims (12)

A cured film-forming composition containing (A) a photoalignment group and a hydroxyl group selected from a cinnamyl group, a chalcone group, a coumarin group, an anthracenyl group, and an azophenyl group, and a C=C double The polymer, (B) cross-linking agent, and (C) cross-linking catalyst that impart the aforementioned polymerizable group containing a C=C double bond are the following (SC-1) and ( Any of SC-2),

(In the formula, X ⁴ represents a polymerizable group containing a C=C double bond, L ¹ represents a covalent bond, ether bond, ester bond, amide bond, urea bond or urethane bond, Q ¹ and Q ³ Each independently represents an alkylene group having 2 to 10 carbon atoms, Q ² represents a divalent group having a structure derived from a dicarboxylic anhydride, and n represents a natural number from 1 to 10). The cured film-forming composition of claim 1, wherein the photo-alignment group of the component (A) is a functional group having a photodimerization or photoisomerization structure. The cured film-forming composition of Claim 1 or Claim 2, wherein the photo-alignment group of component (A) is a cinnamonyl group. The cured film forming composition of Claim 1 or Claim 2, wherein the photo-alignment group of component (A) is a group having an azobenzene structure. The cured film-forming composition of Claim 1 or Claim 2, which further contains (D) a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amine group, and an alkoxysilyl group. things. The cured film-forming composition of Claim 1 or Claim 2, wherein the polymer of component (A) contains a structural unit having a hydroxyl group and a structural unit having a polymerizable group containing a C=C double bond, and the polymer having a hydroxyl group The proportion of the structural units present is 20 mol% or more relative to 100 mol% of the total structural units of the polymer, and the proportion of the structural units having a polymerizable group containing a C=C double bond is relatively Based on 100 mol% of all structural units of the polymer, it is 5 mol% or more. The cured film-forming composition of Claim 1 or Claim 2, wherein 100 parts by mass of the polymer of component (A) contains 5 to 500 parts by mass of the cross-linking agent of component (B). The cured film forming composition of Claim 1 or Claim 2, wherein 100 parts by mass of the polymer of component (A) contains 0.01 to 20 parts by mass of the cross-linking catalyst of component (C). A cured film obtained from the cured film-forming composition according to any one of claims 1 to 8. An optical film having the cured film according to claim 9. An alignment material formed using the cured film of claim 9. A phase difference material formed using the cured film according to claim 9.