JPWO2019189189A1 - Hardened film forming composition, alignment material and retardation material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured film forming composition for forming a cured film having excellent liquid crystal orientation and adhesion, the cured film thereof, an optical film formed by using the cured film, an alignment material and a retardation material. provide. A cured film containing (A) a polymer having a photo-oriented group, a hydroxy group, and a polymerizable group containing a C = C double bond, (B) a cross-linking agent, and (C) a cross-linking catalyst. A forming composition, a cured film formed from the cured film forming composition, an optical film formed by using the cured film, an alignment material and a retardation material. [Selection diagram] None

Description

The present invention relates to a cured film forming composition, a cured film, an optical film, an alignment material and a retardation material for forming a cured film for aligning liquid crystal molecules. In particular, the present invention uses a patterned retardation material used for a circularly polarized glasses type 3D display, a retardation material used for a circular polarizing plate used as an antireflection film for an organic EL display, and the retardation material. The present invention relates to a cured film forming composition, a cured film, an optical film and an alignment material useful for making.

In the case of a circularly polarized glasses type 3D display, a retardation material is usually arranged on a display element that forms an image such as a liquid crystal panel. In this retardation material, a plurality of two types of retardation regions having different retardation characteristics are regularly arranged to form a patterned retardation material. Hereinafter, in the present specification, a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

The patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal, as disclosed in Patent Document 1. The optical patterning of a retardation material composed of a polymerizable liquid crystal utilizes a photoalignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-oriented material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photoalignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different orientation control directions of the liquid crystal are formed. A solution-like retardation material containing a polymerizable liquid crystal is applied onto the photoalignment film to realize the orientation of the polymerizable liquid crystal. Then, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

The antireflection film of the organic EL display is composed of a linear polarizing plate and a 1/4 wavelength retardation plate, and the external light directed to the panel surface of the image display panel is converted into linearly polarized light by the linear polarizing plate, followed by 1/4 wavelength. Converted to circularly polarized light by the retardation plate. Here, the external light due to this circular polarization is reflected by the surface of the image display panel or the like, but the rotation direction of the polarizing surface is reversed at the time of this reflection. As a result, the reflected light is converted from the 1/4 wavelength retardation plate into linearly polarized light in the direction shaded by the linear polarizing plate, and then shielded by the subsequent linear polarizing plate, which is the opposite of the light reflected at the time of arrival. As a result, the emission to the outside is remarkably suppressed.

Regarding this 1/4 wavelength retardation plate, Patent Document 2 describes that the optical film has reverse dispersion characteristics by forming a 1/4 wavelength retardation plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate. The method of constructing by is proposed. In the case of this method, in a wide wavelength band used for displaying a color image, an optical film can be formed by a reverse dispersion characteristic by using a liquid crystal material having a positive dispersion characteristic.

Further, in recent years, as a liquid crystal material applicable to this retardation layer, a material having a reverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such a reverse dispersion characteristic, instead of forming a 1/4 wavelength retardation plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate and forming a 1/4 wavelength retardation plate by two retardation layers, a retardation layer Can be configured with a single layer to ensure inverse dispersion characteristics, whereby an optical film capable of securing a desired phase difference in a wide wavelength band can be realized with a simple configuration.

An alignment layer is used to orient the liquid crystal. As a method for forming an alignment layer, for example, a rubbing method and a photo-alignment method are known. The photo-alignment method does not generate static electricity or dust, which is a problem of the rubbing method, and can quantitatively control the alignment process. Is useful in.

In the formation of an alignment material using the photo-alignment method, acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chains are known as usable photo-alignment materials. It has been reported that these resins exhibit the ability to control the orientation of liquid crystals (hereinafter, also referred to as liquid crystal orientation) by irradiating with polarized UV (see Patent Documents 5 to 7).

Further, the alignment layer is required to have solvent resistance as well as liquid crystal alignment ability. For example, the alignment layer may be exposed to heat or a solvent during the manufacturing process of the retardation material. When the alignment layer is exposed to a solvent, the liquid crystal alignment ability may be significantly reduced.

Therefore, for example, in Patent Document 8, in order to obtain a stable liquid crystal alignment ability, a liquid crystal aligning agent containing a polymer component having a structure capable of a cross-linking reaction by light and a structure cross-linked by heat, and light are used. A liquid crystal alignment agent containing a polymer component having a structure capable of a cross-linking reaction and a compound having a structure cross-linked by heat has been proposed.

In addition, the alignment layer is required to have close contact with the liquid crystal layer. If the adhesion between the alignment layer and the liquid crystal layer formed on the alignment layer is not sufficient, the liquid crystal layer may be peeled off, for example, in the winding step at the time of manufacturing the retardation film.

Japanese Unexamined Patent Publication No. 2005-49965 Japanese Unexamined Patent Publication No. 10-68816 U.S. Pat. No. 8119026 JP-A-2009-179563 Japanese Patent No. 361342 Japanese Unexamined Patent Publication No. 2009-058584 Special Table 2001-517719 Japanese Patent No. 4207430

The present invention has been made based on the above findings and examination results. That is, an object of the present invention is to form a cured film used for forming an alignment material which has excellent solvent resistance, can orient a polymerizable liquid crystal with high sensitivity, and has excellent adhesion to a liquid crystal layer. It is to provide a cured film forming composition for this.
Another object of the present invention is to provide an optical film having the cured film, an alignment material formed by using the cured film or the optical film, and a retardation material.

Other objects and advantages of the present invention will become apparent from the description below.

The first aspect of the present invention is
(A) A polymer having a photo-oriented group, a hydroxy group, and a polymerizable group containing a C = C double bond.
The present invention relates to a cured film-forming composition containing (B) a cross-linking agent and (C) a cross-linking catalyst.
In the first aspect of the present invention, the photooriented group of the component (A) is preferably a functional group having a structure of photodimerization or photoisomerization.
In the first aspect of the present invention, the photooriented group of the component (A) is preferably a cinnamoyl group or a group having an azobenzene structure.
In the first aspect of the present invention, it is preferable to further contain a polymer having at least one group selected from the group consisting of (D) hydroxy group, carboxyl group, amide group, amino group and alkoxysilyl group.
In the first aspect of the present invention, the polymer of the component (A) contains a structural unit having a hydroxy group and a structural unit having a polymerizable group containing a C = C double bond, and the structural unit having the hydroxy group. The abundance ratio of the structural unit having a polymerizable group containing a C = C double bond is 20 mol% or more with respect to 100 mol% of the total structural units of the polymer. It is preferably 5 mol% or more with respect to 100 mol% of all structural units.
In the first aspect of the present invention, the cured film-forming composition preferably contains 5 parts by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A).
In the first aspect of the present invention, the cured film-forming composition preferably contains 0.01 parts by mass to 20 parts by mass of the component (C) based on 100 parts by mass of the 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, which is formed by using the cured film of the second aspect of the present invention.

A fifth aspect of the present invention relates to a retardation material, which is formed by using the cured film of the second aspect of the present invention.

According to the present invention, a cured film having excellent solvent resistance, capable of orienting a polymerizable liquid crystal with high sensitivity, and having excellent adhesion to a liquid crystal layer, and a cured film forming composition suitable for forming the cured film. Can be provided.
Further, according to the present invention, it is possible to provide an optical film having the cured film, and an alignment material and a retardation material formed by using the cured film or the optical film.

As described above, there is a demand for a cured film (aligning material) having excellent solvent resistance, capable of orienting a polymerizable liquid crystal with high sensitivity, and having excellent adhesion to a liquid crystal layer. Then, there is a demand for a cured film forming composition suitable for forming a cured film (aligning material) having such performance.

As a result of diligent studies in order to meet the above requirements, the present inventor has a cured film obtained from a cured film forming composition having a specific composition, which has excellent solvent resistance, high sensitivity and polymerizable property. It has been found that the liquid crystal can be oriented and can be used as an alignment material having excellent adhesion to the liquid crystal layer.

Hereinafter, the cured film-forming composition of the present invention will be described in detail with reference to specific examples of components and the like. Then, the cured film and the alignment material of the present invention using the cured film forming composition of the present invention, the retardation material and the liquid crystal display element formed by using the alignment material, and the like will be described.

<Cured film forming composition>
The cured film-forming composition of the present invention is a polymer having a photo-oriented group, a hydroxy group, and a polymerizable group containing a C = C double bond, which is a component (A), and a cross-linking which is a component (B). It contains an agent and a cross-linking catalyst which is a component (C). Further, it can contain a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, which are the components (D). Furthermore, other additives can be contained as long as the effects of the present invention are not impaired. In addition, it can contain a solvent.
The details of each component will be described below.

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

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

In the present invention, the acrylic copolymer refers to a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as an acrylic acid ester, a methacrylate ester, and styrene.

An acrylic copolymer having a photo-oriented group of the component (A), a hydroxy group, and a polymerizable group containing a C = C double bond (hereinafter, also referred to as a specific copolymer) has such a structure. Any acrylic copolymer may be used, and the type of the main chain skeleton and side chains of the polymer constituting the acrylic copolymer is not particularly limited.

Examples of the photo-oriented group include a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group and the like. Of these, a cinnamoyl group is preferable because of its high transparency in the visible light region and high photodimerization reactivity. Examples of the more preferable cinnamoyl group and the substituent containing the cinnamoyl structure include the structure represented by the following formula [1] or the formula [2]. In the present specification, the group in which the benzene ring in the cinnamoyl group is a naphthalene ring is also included in the "cinnamoyl group" and the "substituent containing a cinnamoyl 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. At that time, the phenyl group and the biphenyl group may be substituted with 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, and a cyclohexyl group. At that time, the alkyl group, phenyl group, biphenyl group, and cyclohexyl group having 1 to 18 carbon atoms are selected from covalent bonds, ether bonds, ester bonds, amide bonds, urea bonds, urethane bonds, amino bonds, carbonyl groups, or combinations thereof. A plurality of species may be bound via the bond of one or more selected species.

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

The hydroxy group is a site that binds to the cross-linking agent which is the component (B) by heating. Further, the polymer of the present invention may have a thermally crosslinkable moiety other than the hydroxy group, specifically, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and the like.
The abundance ratio of the structural unit having a hydroxy group in the polymer of the component (A) is preferably 20 mol% or more with respect to 100 mol% of the total structural unit of the polymer. When the content is 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 photo-orientation and can have excellent orientation sensitivity.
Here, when the polymer of the component (A) contains a structural unit having two or more hydroxy groups, the abundance ratio of the structural unit having a hydroxy group is the (hydroxy group) per 100 mol of the total structural unit of the polymer. (Number of moles of structural unit having) × (number of hydroxy groups contained in the structural unit).

The acrylic copolymer of the component (A) preferably has a weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight is more than 200,000 and is excessive, the solubility in a solvent may be lowered and the handleability may be lowered, while the weight average molecular weight is less than 3,000 and is too small. In some cases, the solvent resistance may decrease or the heat resistance may decrease due to insufficient curing during heat curing.

Examples of the method for producing an acrylic copolymer having a photo-oriented group of the component (A), a hydroxy group, and a polymerizable group containing a C = C double bond include the following methods.

In the method 1 for producing the component (A), after copolymerizing a monomer having a photodimerization site and a monomer having an epoxy group, the epoxy group of the obtained copolymer is double-bonded with a carboxyl group and C = C. It is a method of reacting a compound having a polymerizable group containing.

In the method 2 for producing the component (A), after copolymerizing a monomer having a photodimerization site and a monomer having a carboxyl group, an epoxy group and a C = C double bond are attached to the carboxyl group of the obtained copolymer. It is a method of reacting a compound having a polymerizable group containing.

Examples of the monomer having a photodimerization site include a monomer having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group and the like. Of these, a monomer having a cinnamoyl group is particularly preferable because of its high transparency in the visible light region and high photodimerization reactivity.

Of these, a monomer having a cinnamoyl group having a structure represented by the above formula [1] or the above formula [2] and a monomer having a substituent containing a cinnamoyl structure is more preferable. Specific examples of such monomers are 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. At that time, the phenyl group and the biphenyl group may be substituted with either a halogen atom or a cyano group.
L ¹ and L ² independently represent covalent bonds, ether bonds, ester bonds, amide bonds, urea bonds or urethane bonds, respectively.

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, and a cyclohexyl group. At that time, the alkyl group, phenyl group, biphenyl group, and cyclohexyl group having 1 to 18 carbon atoms may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

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

The formula [3] and the formula [4], ^{X 4} represents a polymerizable group. Specific examples of this polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, a methacrylamide group and the like.

In the above formulas [3] and [4], A is any one of the formulas [A1], the formula [A2], the formula [A3], the formula [A4], the formula [A5] and the formula [A6] in the same manner as described above. Represents.

Examples of the monomer having a polymerizable group containing a C = C double bond and a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, and mono- (2- (2-). (Methyloxy) ethyl) phthalate, mono- (2- (acryloyloxy) ethyl) hexahydrophthalate, mono- (2- (methacryloyloxy) ethyl) hexahydrophthalate, mono- (2- (acryloyloxy) ethyl) succinate , Mono- (2- (methacryloyloxy) ethyl) succinate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylicamide, N- (carboxyphenyl) acrylamide and ω-carboxy-polycaprolactone mono (meth) acrylate Can be mentioned. Examples of these monomers include "light ester HO-MS", "light acrylate HOA-MS (N)", "light acrylate HOA-HH (N)" and "light acrylate HOA-MPL (N)". (Above, product name manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-5300, Aronix M-5400 (above, product name manufactured by Toa Synthetic Co., Ltd.), A-SA, SA (above, Shin Nakamura Chemical Industry Co., Ltd.) ), Commercial name) can be used.

Examples of the monomer having a polymerizable group containing a C = C double bond and an epoxy group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl methacrylate glycidyl ether, allyl glycidyl ether, o-vinylbenzyl glycidyl ether, and m-. Vinyl benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxiside. Be done.

Here, in the production of the polymer as the component (A), at least one of the monomer having an epoxy group and the monomer having a carboxyl group as a raw material is a polymerizable group and a group selected from an epoxy group and a carboxyl group. It is preferable to select one having a spacer in between. By selecting such a raw material, the obtained cured film of the present invention has better adhesion to the liquid crystal layer.

式中、Ｘ^４は重合性基を表し、この重合性基の具体例としては、例えば、アクリロイル基、メタクリロイル基、スチレン基、マレイミド基、アクリルアミド基、メタクリルアミド基等が挙げられる。Ｌ^１は共有結合、エーテル結合、エステル結合、アミド結合、尿素結合又はウレタン結合を表す。Ｑ^１およびＱ^３はそれぞれ独立に炭素原子数２乃至１０のアルキレン基を表し、Ｑ^２はジカルボン酸無水物由来の構造を有する二価の基を表す。ｎは１〜１０の自然数を表す。The preferred structure of the spacer and the monomer having a carboxyl group is one of the following (SC-1) and (SC-2).

Wherein, X ⁴ represents a polymerizable group, the specific examples of the polymerizable group is, for example, an acryloyl group, a methacryloyl group, styrene group, a maleimide group, acrylamide group, and a methacrylamide group. L ¹ represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a 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 dicarboxylic acid anhydride. n represents a natural number from 1 to 10.

Examples of the monomer having such a spacer and a carboxyl group include mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and mono- (2- (acryloyloxy) ethyl). Hexahydrophthalate, mono- (2- (methacryloyloxy) ethyl) hexahydrophthalate, mono- (2- (acryloyloxy) ethyl) succinate, mono- (2- (methacryloyloxy) ethyl) succinate and ω-carboxy-poly Caprolactone mono (meth) acrylate is preferred. A polyfunctional acrylate having a carboxyl machine is also preferable. Commercially available products include, for example, "light ester HO-MS", "light acrylate HOA-MS (N)", "light acrylate HOA-HH (N)" and "light acrylate HOA-MPL (N)". Commercially available products can be used as (above, trade name manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-5300, and Aronix M-5400 (above, trade name manufactured by Toa Synthetic Co., Ltd.).

式中、Ｘ^４は重合性基を表し、この重合性基の具体例としては、例えば、アクリロイル基、メタクリロイル基、スチレン基、マレイミド基、アクリルアミド基、メタクリルアミド基等が挙げられる。Ｌ^１は共有結合、エーテル結合、エステル結合、アミド結合、尿素結合又はウレタン結合を表す。Ｑ^１は炭素原子数２乃至１０のアルキレン基を表す。The preferred structure of the spacer and the monomer having an epoxy group is represented by the following (SE-1).

Wherein, X ⁴ represents a polymerizable group, the specific examples of the polymerizable group is, for example, an acryloyl group, a methacryloyl group, styrene group, a maleimide group, acrylamide group, and a methacrylamide group. L ¹ represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond. Q ¹ is an alkylene group having 2 to 10 carbon atoms.

Examples of the monomer having such a spacer and an epoxy group include 4-hydroxybutyl methacrylate glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.

式中、Ｘ^４は重合性基を表し、この重合性基の具体例としては、例えば、アクリロイル基、メタクリロイル基、スチレン基、マレイミド基、アクリルアミド基、メタクリルアミド基等が挙げられる。Ｌ^１は共有結合、エーテル結合、エステル結合、アミド結合、尿素結合又はウレタン結合を表す。Ｑ^４は（ｍ＋１）価の有機基を表し、ｍは２〜１０の自然数を表す。The monomer having a polymerizable group containing a C = C double bond and a carboxyl group for grafting to the epoxy group of the polymer is a polyfunctional acrylate having a carboxyl group represented by (SC-3) below. Is also preferable.

Wherein, X ⁴ represents a polymerizable group, the specific examples of the polymerizable group is, for example, an acryloyl group, a methacryloyl group, styrene group, a maleimide group, acrylamide group, and a methacrylamide group. L ¹ represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond. Q ⁴ are represent (m + 1) -valent organic group, m represents a natural number of 2 to 10.

As such a compound, those commercially available as Aronix M-510 and M-520 (all manufactured by Toagosei Co., Ltd., trade name) can be used.

The amount of the monomer having a photodimerization site and the monomer having an epoxy group used to obtain the specific copolymer according to the production method 1 is based on the total amount of all the monomers used to obtain the specific copolymer. It is preferable that the monomer having a quantification site is 40% by mass to 95% by mass and the monomer having an epoxy group is 5% by mass 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 orientation can be imparted. On the other hand, when it is 95% by mass or less, sufficient thermosetting property can be imparted, and high sensitivity and good liquid crystal orientation can be maintained.

The amount of the monomer having a photodimerization site and the monomer having a carboxyl group used to obtain the specific copolymer according to the production method 2 is the epoxy group in the amount of the monomer having the photodimerization site and the monomer having an epoxy group described above. According to the amount of monomer used.

Further, in the cured film-forming composition of the present invention, when a polymer serving as a precursor of a specific copolymer is obtained, any of a photodimerization site, an epoxy group and a carboxyl group (hereinafter, these are also referred to as specific functional groups). A copolymerizable monomer (hereinafter, also referred to as a monomer having a non-reactive functional group) can be used in combination.

Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic acid anhydrides, styrene compounds and vinyl compounds.
Specific examples of the above-mentioned monomers will be given below, but the present invention is not limited thereto.

Examples of the acrylic acid ester compound described above include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, and 2,2,2-trifluoroethyl. Acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2- Examples thereof include adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound described above include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl. Methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2- Examples thereof include adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate and the like.

Examples of the vinyl compounds described above include methyl vinyl ether, benzyl vinyl ether, vinylnaphthalene, vinylcarbazole, allylglycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-. Examples thereof include hexene and 1,7-octadiene monoepoxiside.

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

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

The method for obtaining a polymer that is a precursor of the specific copolymer used in the cured film-forming composition of the present invention is not particularly limited, and for example, a monomer having a specific functional group selected from a photodimerization site, an epoxy group and a carboxyl group. It is obtained by carrying out a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent in which a monomer having a non-reactive functional group and a polymerization initiator and the like coexist, if desired. At that time, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having a non-reactive functional group used if desired, a polymerization initiator and the like. Specific examples include the solvents described in the solvents described below.

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 is a polymer having an epoxy group as described above and a specific carboxyl. It can be synthesized by reacting a compound having a group and a polymerizable group containing a C = C double bond, preferably in the presence of a catalyst, preferably in a suitable 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 with respect to 1 mol of the epoxy group contained in the polymer having an epoxy group. It is ~ 0.9 mol, more preferably 0.05 to 0.8 mol, still more preferably 0.1 to 0.7 mol.

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 is a polymer having a carboxyl group as described above and a specific epoxy. It can be synthesized by reacting a compound having a group and a polymerizable group containing a C = C double bond, preferably in the presence of a catalyst, preferably in a suitable 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 with respect to 1 mol of the carboxyl group contained in the polymer having a carboxyl group. It is ~ 0.9 mol, more preferably 0.05 to 0.8 mol, still more preferably 0.1 to 0.7 mol.

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

Examples of the organic base include 1-2 secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrol; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and the like. Tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide can be mentioned. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; and quaternary organic amines such as tetramethylammonium hydroxide. preferable.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine; 2-methylimidazole and 2-n-heptylimidazole. , 2-n-Undecylimidazole, 2-phenylimidazole, 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-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimerite, 1- (2-cyanoethyl) ) -2-phenylimidazolium trimerite, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1') )] Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1')] ethyl-s-triazine, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1') ')] Imidazole compounds such as the isocyanuric acid adduct of ethyl-s-triazine; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide , Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra Tertiary phosphonium salts such as -n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate; 1,8-diazabicyclo [5.4. 0] Diazabicycloalkenes such as undecene-7 and its organic acid salts; organic metal compounds such as zinc octylate, tin octylate, aluminum acetylacetone complexes; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, Tertiary ammonium salts such as tetra-n-butylammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and ferric chloride; addition of dicyandiamides and amines to epoxy resins High melting point dispersion type latent curing accelerator such as amine-added type accelerator; microcapsule type latent curing agent such as imidazole compound, organic phosphorus compound and quaternary phosphonium salt whose surface is coated with a polymer. Sexual curing accelerator; amine salt type latent curing accelerator; high temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt, brensted acid salt, etc. it can.
Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.

The ratio of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, still more preferably 100 parts by mass with respect to 100 parts by mass of the polymer having an epoxy group or the polymer having a carboxyl group. Is 0.1 to 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. Of these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferable from the viewpoint of solubility of raw materials and products and ease of purification of products. The solvent is used in an amount such that the solid content concentration (the ratio of the mass of the components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more, more preferably 5 to 50% by mass. Will be done.

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 component (A) 3>
In the method 3 for producing the component (A), a polymer having an epoxy group in the side chain is reacted with a silicate derivative and a compound having the above-mentioned carboxyl group and a polymerizable group containing a C = C double bond. The method.

The polymer having an epoxy group in the side chain may be, for example, a polymer of the above-mentioned monomer having an epoxy group, or the above-mentioned monomer having an epoxy group and the above-mentioned monomer having a non-reactive functional group. It may be a copolymer.

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

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

As the polymer having an epoxy group in the side chain, a commercially available product may be used. Examples of such commercially available products include EHPE3150, EHPE3150CE (above, manufactured by DIC CORPORATION), UG-4010, UG-4035, UG-4040, UG-4070 (above, ARUFON series manufactured by Toa Synthetic Co., Ltd.), ECN- 1299 (manufactured by Asahi Kasei Corporation), DEN431, DEN438 (manufactured by Dow Chemical Corporation), jER-152 (manufactured by Mitsubishi Chemical Corporation), Epicron N-660, N-665, N-670, N-673, N-695, N-740, N-770, N-775 (above, manufactured by DIC Corporation), EOCN-1020, EOCN-102S, EOCN-104S (above, manufactured by Nippon Kayaku Co., Ltd.), etc. Be done.

（式中、Ｒ^１は水素原子、ハロゲン原子、炭素原子数１乃至６のアルキル基、炭素原子数１乃至６のアルコキシ等を表す。）のいずれかで表される化合物等を挙げることができる。
また、カルボキシル基を有する桂皮酸誘導体として、上述の式［３］で表されるモノマーにおいて、Ｘ^１が水素原子である化合物も好適に用いられる。Examples of the cinnamic acid derivative 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 having 1 to 6 carbon atoms, etc.). ..
Further, as the cinnamic acid derivative having a carboxyl group, a compound in which ^{X 1} is a hydrogen atom in the above-mentioned monomer represented by the formula [3] is also preferably used.

The cinnamic acid derivative can be synthesized by appropriately combining conventional methods of organic chemistry.

Here, the compound (monomer) having a polymerizable group containing a carboxyl group and a C = C double bond is a compound (monomer) having a spacer between the group having a C = C double bond and the carboxyl group as described above. It is preferable to select.

The method for reacting a polymer having an epoxy group in the side chain with a compound having a silicate derivative and the above-mentioned polymerizable group containing a carboxyl group and a C = C double bond is as described above. At that time, the polymer having an epoxy group in the side chain may be reacted together with the carcinate derivative and the compound having the above-mentioned carboxyl group and a polymerizable group containing a C = C double bond. , May be reacted separately.

The abundance ratio of the structural unit having a polymerizable group containing a C = C double bond in the polymer of the component (A) is preferably 5 mol% or more per 100 mol of the total structural unit of the polymer, preferably 10 mol. It is more preferably% or more. If the total is less than 5 mol%, the adhesion to the liquid crystal layer may be insufficient.
Here, when the polymer of the component (A) contains a structural unit having a polymerizable group containing two or more C = C double bonds, the structural unit having a polymerizable group containing a C = C double bond The abundance ratio of is defined as (the number of moles of the structural unit having a polymerizable group containing a C = C double bond) x (the C = C double bond contained in the structural unit) per 100 mol of the total structural unit of the polymer. (Number of polymerizable groups).

In this way, a solution containing a polymer having a photo-oriented group, a hydroxy group, and a polymerizable group containing a C = C double bond, which is the component (A), is obtained. This solution may be used as it is for the preparation of the liquid crystal alignment agent, the polymer contained in the solution may be isolated and then used for the preparation of the liquid crystal alignment agent, or the isolated polymer may be purified. It may be used for the preparation of a liquid crystal aligning agent.

Further, the solution of the specific copolymer obtained as described above is added under stirring with diethyl ether, water or the like to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Then, it can be made into a powder of a specific copolymer by drying at room temperature or by heating. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the cured film-forming composition of the present invention, the powder of the specific copolymer may be used as it is as the component (A), or the powder may be redissolved in, for example, a solvent described later to prepare a solution. You may use it.

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

As described above, in the present invention, a high molecular weight specific copolymer can be used as the component (A). Further, the 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 the component (B). More specifically, the component (B) is a cross-linking agent that reacts with the above-mentioned components (A) and (C). The component (B) is bonded to the thermally crosslinkable group (particularly the hydroxy group) of the polymer which is the component (A) and the hydroxy group contained in the component (C). Then, the cured film forming composition of the present embodiment can form an alignment material having high photoreaction efficiency as a cured film.

Examples of the cross-linking agent as the component (B) include compounds such as an epoxy compound, a methylol compound and an isocyanate compound, and a methylol compound is preferable. Among them, as the cross-linking agent as the component (B), a compound having two or more groups that form a cross-link with the thermally cross-linkable functional group of the component (A) is preferable, and for example, two methylol groups or two alkoxymethyl groups are preferable. It is preferable that the cross-linking agent has the above. Examples of the compound having these groups include methylol compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine and alkoxymethylated melamine.

Specific examples of the methylol compound described above include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, alkoxymethylated melamine, tetra (alkoxymethyl) bisphenol and tetra (hydroxymethyl) bisphenol.

Specific examples of alkoxymethylated glycol uryl include 1,3,4,6-tetrax (methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by DIC Co., Ltd. (high condensation type, trade name: Beccamin () Registered trademarks) J-300S, P-955, N) and the like.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As commercial products, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark)). ) 506, 508), Sanwa Chemical Co., Ltd. methoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS- 001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MX-45, MX-410, MX-302) ) Etc. can be mentioned.

Examples of tetra (alkoxymethyl) bisphenol and tetra (hydroxymethyl) bisphenol include tetra (alkoxymethyl) bisphenol A and tetra (hydroxymethyl) bisphenol A.

The cross-linking agent as the component (B) is a compound obtained by condensing such a melamine compound, a urea compound, a glycoluryl compound and a benzoguanamine compound in which the hydrogen atom of the amino group is replaced with a methylol group or an alkoxymethyl group. It may be. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.

Further, as a cross-linking agent for the component (B), a hydroxymethyl group (that is, a methylol group) or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylate, N-ethoxymethylacrylamide, N-butoxymethylmethacrylate and the like. Polymers prepared using acrylamide compounds or methacrylic amide compounds substituted with are also available.

Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.

Further, 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 acrylic group, a methacryl 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 this specific functional group with a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound), the polymer as the component (B) is polymerizable with a C = C double bond. The group can be introduced.

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

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

Monomers having a glycidyl group include, for example, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and 1,7. -Octadiene monoepoxide etc. can be mentioned.

Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and 2,3-. Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly Examples thereof include (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

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

Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.

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

In the above-mentioned reaction, the preferable combination of the specific functional group and the functional group of the specific compound and participating in the reaction is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, and a phenolic hydroxy group and an epoxy group. It is a carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride. Further, a more preferable combination is a carboxyl group and a glycidyl methacrylate, or a hydroxy group and an isocyanate ethyl methacrylate.

The weight average molecular weight (polystyrene equivalent value) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, and more preferably 3,000 to 150,000. , 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 the component (B) in the cured film forming composition of the present invention is 5 parts by mass to 500 parts by mass based on the total amount of 100 parts by mass of the polymer of the component (A) and the cross-linking catalyst of the component (C). It is preferably parts by mass, 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 orientation may decrease. On the other hand, if the content is excessive, the liquid crystal orientation and storage stability may decrease.

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

When an acid or a thermoacid generator is used as the component (C), the component (C) is a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, a compound that thermally decomposes during prebaking or postbaking to generate an acid, that is, a temperature of 80. The compound is not particularly limited as long as it is a compound that thermally decomposes at ° C. to 250 ° C. to generate an acid.

Such compounds include, for example, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphasulfonic acid, trifluo. Lomethane sulfonic acid, p-phenol sulfonic acid, 2-naphthalene sulfonic acid, mesitylen sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene sulfonic acid, 1H, 1H, 2H, 2H-Perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, sulfonic acid such as dodecylbenzene sulfonic acid or hydrates and salts thereof, etc. Can be mentioned.

Examples of compounds that generate acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-phenylentris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p- Examples thereof include tosylate, N-ethyl-4-toluenesulfoneamide, and compounds represented by the following formulas [TAG-1] to [TAG-41].

The content of the component (C) in the cured film-forming composition according to the embodiment of the present invention is 0.01 part by mass to 20 parts by mass, preferably 0.% by mass, based on 100 parts by mass of the polymer which is the component (A). It is 01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 8 parts by mass, and further preferably 0.1 parts by mass to 6 parts by mass. By setting the content of the component (C) to 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted. Further, when the content is 20 parts by mass or less, the storage stability of the cured film forming composition can be improved.

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

Examples of the polymer as the component (D) include acrylic polymers, urethane-modified acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols. Examples thereof include polymers having a linear structure or a branched structure such as polyalkyleneimine, polyallylamine, celluloses (cellulose or a derivative thereof), phenol novolac resin, and cyclic polymers such as cyclodextrins.

Of these, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as an acrylic acid ester, a methacrylic acid ester, or styrene can be applied. The synthesis method includes a monomer having a hydroxy group, a monomer having a carboxyl group, a monomer having an amide group, a monomer having an amino group, and an alkoxysilyl group exemplified in the chapters of the components (A) and (B). A simple method is to (co) polymerize a monomer having at least one group selected from the group consisting of monomers and, if desired, other monomers by the method described in the chapters (A) and (B) above. Is.

The acrylic polymer, which is an example of the component (D), preferably has a weight average molecular weight of 3000 to 200,000, more preferably 4000 to 150,000, and even more preferably 5000 to 100,000.

As a preferred example of the component (D), a polyether polyol obtained by adding propylene oxide, polyethylene glycol, polypropylene glycol or the like to a polyhydric alcohol such as polyethylene glycol, polypropylene glycol, propylene glycol or bisphenol A, triethylene glycol or sorbitol. Things can be mentioned. Specific examples of the polyether polyol include ADEKA Corporation's Adeka Polyether P series, G series, EDP series, BPX series, FC series, CM series, NOF Corporation's Uniox (registered trademark) HC-40, and NOF Corporation. HC-60, ST-30E, ST-40E, G-450, G-750, Uniol® 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 and the like can be mentioned.

As a polyester polyol which is a preferable example of the component (D), a polyvalent carboxylic acid such as adipic acid, sebacic acid and isophthalic acid is reacted with a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol and polypropylene glycol. Things can be mentioned. 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, OD-X manufactured by DIC Corporation. -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, Polyester manufactured by Kuraray Co., Ltd. P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510 , F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.

Examples of the polycaprolactone polyol which is a preferable example of the component (D) include ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of the polycaprolactone polyol include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC Corporation, and Praxel (registered trademark) 205, L205AL, 205U manufactured by Daicel Chemical Co., Ltd. Examples thereof include 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like.

Examples of the polycarbonate polyol which is a preferable example of the component (D) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Specific examples of the polycarbonate polyol include Daicel Corporation's Praxel® CD205, CD205PL, CD210, CD220, and Kuraray Corporation's C-590, C-1050, C-2050, C-2090, and C-3090. And so on.

Preferred examples of the component (D) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose and the like. For example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

Cyclodextrins which are preferable examples of the component (D) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γcyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl-γ-. Methylated cyclodextrin such as cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 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 Examples thereof include hydroxyalkylcyclodextrins such as −dihydroxypropyl-γ-cyclodextrins.

As a urethane-modified acrylic polymer which is a preferable example of the component (D), as a commercially available product, Acryt (registered trademark) 8UA-017, 8UA-239, 8UA-239H, 8UA-140, 8UA-146 manufactured by Taisei Fine Chemicals Co., Ltd. , 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, 8UA-366 and the like.

Examples of the phenol novolac resin, which is a preferable example of the component (D), include a phenol-formaldehyde polycondensate.

In the composition of the present invention, the polymer of the component (D) may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.

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

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

[(E) component]
The composition of the present invention can further contain a low molecular weight photoalignment component as the component (E). By containing the low-molecular-weight photo-alignment component, the abundance of photo-orientation groups on the surface layer of the alignment film is increased, which has the effect of improving the orientation sensitivity. Examples of such a low molecular weight photoalignment component include a monomer represented by the formula [3], a monomer represented by the formula [4], and a monomer represented by the formula [3] represented by the section (A) of the present specification. A compound in which the monomer group X ⁴ is replaced with a hydrogen atom, a compound in which the monomer group X ⁴ represented by the formula [4] is replaced with a hydrogen atom, and the above formulas (1-1) to (1-5). Examples thereof include a katsura acid derivative having a carboxyl group represented by any of them.

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

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

[Other additives]
The cured film-forming composition of 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, for example, a sensitizer can be contained. The sensitizer is effective in promoting the photoreaction of the surface cured film of the optical film of the present invention.

Examples of the sensitizer include derivatives such as benzophenone, anthracene, anthraquinone and thioxanthone, and nitrophenyl compounds. Of these, N, N-diethylaminobenzophenone, which is a derivative of benzophenone, and 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacetylene, 4-nitrobiphenyl, 4-nitrocipheric acid, which are nitrophenyl compounds, 4 -Nitrostilbene, 4-nitrobenzophenone, 5-nitroindole are particularly preferred.

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

In the embodiment of the present invention, the ratio of the sensitizer used is preferably 0.1 part by mass to 20 parts by mass, and more preferably 0.2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the component (A). It is 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and if it is too large, the transmittance of the formed cured film may decrease or the coating film may become rough. I have something to do.

In addition, the cured film-forming composition of the embodiment of the present invention contains silane coupling agents, surfactants, rheology modifiers, pigments, dyes, and storage stability as other additives as long as the effects of the present invention are not impaired. It can contain agents, antifoaming agents, antioxidants and the like.

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

Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and 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, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate, isopropanol, N, N -Dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like can be mentioned.

These solvents can be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate. , 3-Methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate are more preferable because they have good film-forming properties and high safety.

<Preparation of cured film forming composition>
The cured film-forming composition of the present invention is a thermosetting cured film-forming composition having photoalignment. As described above, the cured film-forming composition of the present invention is a polymer having a photo-oriented group which is a component (A), a hydroxy group, and a polymerizable group containing a C = C double bond, (B). It contains a cross-linking agent as a component and a cross-linking catalyst as a component (C). If necessary, it contains a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, which are components (D). Then, other additives can be contained and a solvent can be further contained as long as the effects of the present invention are not impaired.

Preferred examples of the cured film forming composition of the present embodiment are as follows.
[1]: A polymer having a photoorientating group as a component (A), a hydroxy group, and a polymerizable group containing a C = C double bond, and 1 based on 100 parts by mass of the polymer as a component (A). 0.01 parts to 20 parts by mass with respect to 100 parts by mass of the cross-linking agent which is the component (B) and the polymer which is the component (A) of 5 parts by mass to 500 parts by mass, preferably 5 parts by mass to 500 parts by mass. A cured film-forming composition containing a cross-linking catalyst which is a component (C) by mass.

[2]: A polymer having a photo-orientating group as a component (A), a hydroxy group, and a polymerizable group containing a C = C double bond, and 1 based on 100 parts by mass of the polymer as a component (A). 0.01 parts to 20 parts by mass with respect to 100 parts by mass of the cross-linking agent which is the component (B) and the polymer which is the component (A) of 5 parts by mass to 500 parts by mass, preferably 5 parts by mass to 500 parts by mass. 5 parts by mass to 500 parts by mass of the hydroxy group, which is a component (D) based on 100 parts by mass of the polymer which is a component (A), contains a cross-linking catalyst and a solvent which are components (C) by mass. A cured film-forming composition containing a polymer having at least one group selected from the group consisting of a carboxyl group, an amide group, an amino group and an alkoxysilyl group, and a solvent.

The blending ratio, preparation method, etc. when the cured film-forming composition of the present embodiment is used as a solution will be described in detail below.

The proportion of the solid content 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, but is 1% by mass to 80% by mass, preferably 2. It is from mass% to 60% by mass, more preferably 3% by mass to 40% by mass. Here, the solid content refers to a composition obtained by removing the solvent from all the components of the cured film forming composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, a solution of the component (A) dissolved in a solvent is provided with a component (B), a component (C), a component (D), a component (E) and / or other additives. Examples thereof include a method of mixing in a ratio to obtain a uniform solution, or a method of further adding and mixing other additives as necessary at an appropriate stage of this preparation method.

In the preparation of the cured film-forming composition of the present invention, the solution of the specific copolymer obtained by the polymerization reaction in the solvent can be used as it is. In this case, for example, the component (B), the component (C), the component (D), the component (E) and / or other additions to the solution prepared by preparing the polymer (acrylic polymer) of the component (A). Add the agent to make a uniform solution. At this time, an additional solvent may be added for the purpose of adjusting the concentration. At this time, the solvent used in the process of preparing the component (A) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.

Further, it is preferable that the prepared solution of the cured film-forming composition is used after being filtered using a filter having a pore size of about 0.2 μm or the like.

As described above, the cured film-forming composition of the present invention comprises a group consisting of a polymer having a photo-oriented group which is a component (A), a hydroxy group, and a polymerizable group containing a C = C double bond. It is composed of at least one selected, a cross-linking agent which is a component (B), and a cross-linking catalyst which is a component (C).

Therefore, the cured film formed from the cured film forming composition of the present invention is formed so that the inside thereof becomes hydrophilic due to the property of the component (A) so that the film structure is stabilized. Then, the photo-oriented group of the component (A) and the polymerizable group containing the C = C double bond in the cured film become unevenly distributed in the vicinity of the surface of the cured film. More specifically, in the polymer of the component (A), the hydrophilic hydroxy group faces the inner side of the cured film, and the hydrophobic photoreactive part and the polymerizable group containing the C = C double bond face the surface side. It is unevenly distributed near the surface of the cured film while taking a facing structure. As a result, the cured film of the present invention realizes a structure in which the proportion of the photoreactive group of the component (A) existing near the surface and the polymerizable group containing the C = C double bond is increased. When the cured film of the present invention is used as an alignment material, the efficiency of the photoreaction for photoalignment can be improved, and the cured film can have excellent orientation sensitivity. Further, it becomes an alignment material suitable for forming a patterned retardation material, and the patterned retardation material produced by using the alignment material can have excellent pattern forming property.

Further, as described above, the cured film forming composition of the present invention contains a cross-linking agent which is a component (B). Therefore, inside the cured film obtained from the cured film-forming composition of the present invention, a cross-linking reaction by a thermal reaction with the component (B) is performed before the photoreaction by the photooriented group of the polymer of the component (A). It can be carried out. As a result, when it is used as an alignment material, it is possible to improve the resistance to the polymerizable liquid crystal coated on it and its solvent.

Further, the polymerizable group containing the C = C double bond of the polymer which is the component (A) is formed on the cured film obtained from the cured film forming composition of the present invention when it is used as an alignment material. It functions to enhance the adhesion between the cured polymerizable liquid crystal layer.

<Hardened film, alignment material and retardation material>
The solution of the cured film forming composition of the present embodiment is applied to a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate). , ITO substrate, etc.) and films (for example, resin films such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film, etc.), bar coat, rotary coating, flow coating, roll coating, etc. , Slit coating, rotary coating following the slit, inkjet coating, printing, etc. to form a coating film, and then heat-drying with a hot plate, an oven, or the like to form a cured film.

As a condition for heating and drying, the curing reaction may proceed to such an extent that the components of the alignment material formed from the cured film do not elute into the polymerizable liquid crystal solution applied thereto. For example, the temperature is 60 ° C. to 200 ° C. , The heating temperature and heating time appropriately selected from the range of 0.4 minutes to 60 minutes are adopted. The heating temperature and heating time are preferably 70 ° C. to 160 ° C., 0.5 minutes to 10 minutes.

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

The cured film thus formed can function as an alignment material, that is, a member for aligning a liquid crystal compound including a polymerizable liquid crystal or the like by irradiating with polarized UV.

As a method of irradiating polarized UV, ultraviolet light to visible light having a wavelength of 150 nm to 450 nm is usually used, and it is carried out by irradiating linearly polarized light from a vertical or diagonal direction at room temperature or in a heated state.

Since the alignment material formed by using the cured film formed from the cured film forming composition of the present invention has solvent resistance and heat resistance, the alignment material is composed of a polymerizable liquid crystal solution on the alignment material. After applying the phase difference material, the phase difference material is brought into a liquid crystal state by heating to the phase transition temperature of the liquid crystal, and is oriented on the alignment material. Then, the retardation material in the desired orientation state can be cured as it is 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 same are used. When the substrate on which the alignment material is formed is a film, the film having the retardation material of the present embodiment is useful as the retardation film. Some retardation materials that form such retardation materials are in a liquid crystal state and take orientation states such as horizontal orientation, cholesteric orientation, vertical orientation, and hybrid orientation on the alignment material, and are required for each. It can be used properly according to the phase difference characteristics.

Further, in the case of producing a patterned retardation material used for a 3D display, a predetermined cured film formed from the cured film forming composition of the present invention is formed on a cured film formed by the above method via a line-and-space pattern mask. From the reference, for example, polarized UV exposure is performed in the direction of +45 degrees, then polarized UV is exposed in the direction of -45 degrees after removing the mask, and two types of liquid crystal alignment regions having different liquid crystal orientation control directions are formed. Form an alignment material. Then, after applying a retardation material composed of a polymerizable liquid crystal solution, 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 in the liquid crystal state is oriented on the alignment material in which two types of liquid crystal alignment regions are formed, and the orientation state corresponding to each liquid crystal alignment region is formed. Then, the retardation material in which such an orientation state is realized is cured as it is, the above-mentioned orientation state is fixed, and a plurality of two types of retardation regions having different retardation characteristics are regularly arranged. A chemical phase difference material can be obtained.

Further, the alignment material formed by using the cured film formed from the cured film forming composition of the present invention can also be used as a liquid crystal alignment film of a liquid crystal display element. For example, using two substrates having the alignment material of the present invention formed as described above, the alignment materials on both substrates are laminated so as to face each other via a spacer, and then between the substrates. A liquid crystal display element in which the liquid crystal is oriented can be manufactured by injecting the liquid crystal.
Therefore, the cured film forming composition of the present embodiment can be suitably used for manufacturing various retardation materials (phase difference films), liquid crystal display elements, and the like.

Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not construed as being limited thereto.

ＣＩＮ２：

[Abbreviations used in 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-butoxymethylacrylamide CIN1:

CIN2:

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

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

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

A-3: 2-Acryloyloxyethyl succinate

<B component>
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

（上記式中、Ｒは、アルキレン基を表す。）<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 example was determined by Shodex Co., Ltd. room temperature gel permeation chromatography (GPC) apparatus (GPC-101), Shodex Co., Ltd. column (KD-803, KD-805). Was measured as follows.
The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene-equivalent values.
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / Standard sample for preparing a calibration curve: Standard polystyrene manufactured by Showa Denko KK (molecular weight approx. 197,000, 55, 100, 12,800, 3,950, 1,260,580) ).

<Synthesis of component A>
<Synthesis example 1>
An acrylic polymer solution was obtained by dissolving 15.0 g of GMA and 0.8 g of AIBN as a polymerization catalyst in 63.0 g of tetrahydrofuran and reacting them under heating under reflux for 20 hours. The acrylic polymer solution was gradually added dropwise to 500.0 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic polymer (P-1). The obtained acrylic polymer had Mn of 6,500 and Mw of 11,000.

<Synthesis example 2>
10.0 g of the epoxy group-containing acrylic polymer (P-1) 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 dibutyl as a polymerization inhibitor. 0.4 g of hydroxytoluene was dissolved in 46.1 g of PM and reacted at 80 ° C. for 20 hours to obtain a solution containing 30% by mass of the acrylic polymer (PA-1). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

<Synthesis Examples 3 to 10>
Synthesis Example 2 except that the types and amounts of the polymer having an epoxy group (acrylic polymer), the compound giving a photoorientation group, and the compound giving a group containing a polymerizable double bond are as shown in Table 1 below. The same procedure was carried out to obtain a solution containing 30% by mass of the polymers (PA-2) to (PA-9). The blanks in Table 1 indicate that the corresponding component was not blended.

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

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

<Example 1>
(A) An amount corresponding to 100 parts by mass in terms of the acrylic polymer (PA-1) of the solution containing 30% by mass of the acrylic polymer (PA-1) obtained in Synthesis Example 2 as a component (B). ) 30 parts by mass of HMM as a component and 3 parts by mass of PTSA as a component (C) are mixed, PM and EA are added thereto, the solvent composition is PM: EA = 100: 30 (mass ratio), and the solid content concentration is 5. A polymer (aligning material) forming composition (A-1) having a mass ratio of 0.0% by mass was prepared.

<Examples 2 to 12 and Comparative Examples 1 to 2>
The types and amounts of each component were set as shown in Table 2, and the same procedure as in Example 1 was carried out to prepare cured film (aligning material) forming compositions A-2 to A-15, respectively. .. The blanks in Table 2 indicate that the corresponding component was not blended.

<Examples 13 to 24 and Comparative Examples 3 to 4>
[Evaluation of orientation]
The cured film (aligning material) forming compositions of Examples 1 to 12 and Comparative Examples 1 and 2 were applied onto a TAC film using a bar coater at a Wet film thickness of 4 μm. Each was heated and dried in a heat circulation type oven at a temperature of 110 ° C. for 60 seconds to form a cured film on the film. Each of the cured films was vertically irradiated with linearly polarized light of 313 nm at ^{an exposure amount of 10 mJ / cm 2} to form an alignment material. A polymerizable liquid crystal solution (RM-1) was applied onto the alignment material on the film using a bar coater at a Wet film thickness of 6 μm. This coating film was dried on a hot plate at a temperature of 90 ° C. for 60 seconds ^{and then exposed at 300 mJ / cm 2} to prepare a retardation material. The retardation material on the produced film was sandwiched between a pair of polarizing plates, and the expression status of the retardation characteristics in the retardation material was observed. Those are described as x in the "Orientation" column. The evaluation results are summarized in Table 3 later.

[Evaluation of adhesion]
The cured film (aligning material) forming compositions of Examples 1 to 12 and Comparative Examples 1 and 2 were applied onto a TAC film using a bar coater at a Wet film thickness of 4 μm. Each was heated and dried in a heat circulation type oven at a temperature of 110 ° C. for 60 seconds to form a cured film on the film. Each of the cured films was vertically irradiated with linearly polarized light of 313 nm at ^{an exposure amount of 10 mJ / cm 2} to form an alignment material. A polymerizable liquid crystal solution (RM-1) was applied onto the alignment material on the film using a bar coater at a Wet film thickness of 6 μm. This coating film was dried on a hot plate at a temperature of 90 ° C. for 60 seconds ^{and then exposed at 300 mJ / cm 2} to prepare a retardation material. The retardation material was cut with a cutter knife so as to form 5 × 5 squares at intervals of 1 mm in length and width. A cellophane tape peeling test was performed on this notch using scotch tape. The evaluation result was "adhesion", and the number of squares remaining in the 25 squares without peeling was described. For example, if it is 25/25, all the cells remain without peeling off, indicating that the adhesion is high. The evaluation results are summarized in Table 3 later.

As shown in Table 3, the retardation materials obtained in Examples 13 to 24 showed good orientation and high adhesion.

On the other hand, the retardation material obtained in Comparative Example 3 showed good orientation, but sufficient adhesion could not be obtained. Further, the retardation material obtained in Comparative Example 4 was insufficient in both orientation and adhesion.

The cured film formed from the cured film forming composition of the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display element and an optically anisotropic film provided inside or outside the liquid crystal display element. It is useful. In particular, the cured film forming composition of the present invention is suitable as a material for forming a cured film used as a patterned retardation material for a 3D display. Further, the cured film forming composition of the present invention is a material for forming a cured film such as a protective film, a flat film and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, particularly a TFT type liquid crystal. It is also suitable as a material for forming an interlayer insulating film of a display element, a protective film of a color filter, an insulating film of an organic EL element, and the like.

Claims (12)

(A) A polymer having a photo-oriented group, a hydroxy group, and a polymerizable group containing a C = C double bond.
A cured film-forming composition containing (B) a cross-linking agent and (C) a cross-linking catalyst. The cured film-forming composition according to claim 1, wherein the photo-oriented group of the component (A) is a functional group having a structure of photodimerization or photoisomerization. The cured film-forming composition according to claim 1 or 2, wherein the photo-oriented group of the component (A) is a cinnamoyl group. The cured film-forming composition according to claim 1 or 2, wherein the photo-oriented group of the component (A) is a group having an azobenzene structure. (D) The cured film according to any one of claims 1 to 4, further containing a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group. Forming composition. The polymer of the component (A) contains a structural unit having a hydroxy group and a structural unit having a polymerizable group containing a C = C double bond, and the abundance ratio of the structural unit having the hydroxy group is the total of the polymer. The abundance ratio of the structural unit having a polymerizable group containing a C = C double bond is 20 mol% or more with respect to 100 mol% of the structural unit with respect to 100 mol% of the total structural unit of the polymer. The cured film-forming composition according to any one of claims 1 to 5, which is 5 mol% or more. The cured film according to any one of claims 1 to 6, which contains 5 parts by mass to 500 parts by mass of a cross-linking agent of the component (B) based on 100 parts by mass of the polymer of the component (A). Forming composition. The invention according to any one of claims 1 to 7, wherein the cross-linking catalyst of the component (C) is contained in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the polymer of the component (A). Cured film forming composition. 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 by using the cured film according to claim 9. A retardation material formed by using the cured film according to claim 9.