JPWO2018131682A1 - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

[Summary] [PROBLEMS] An alignment material having excellent vertical alignment and adhesion, and capable of aligning a polymerizable liquid crystal vertically with high sensitivity even on a resin film, and a retardation material using such an alignment material Providing a cured film forming composition for providing A cured film forming composition comprising (A) a polymer having a vertical orientation group and a polymerizable group containing a C═C double bond, and (B) a radical polymerization initiator, A cured film forming composition, wherein the orientation group is a group represented by the following formula (1). (In the formula [1], Y1 and Y2 represent a single bond or the like, Y3 represents a single bond or an alkylene group having 1 to 15 carbon atoms, and Y4 represents a single bond or a divalent cyclic group or the like. Y5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, n represents an integer of 0 to 4, and when n is 2 or more, Y5 may be the same or different. Y6 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.) [Selection] None

Description

  The present invention relates to a cured film forming composition suitable for a vertical alignment material for vertically aligning liquid crystal molecules. In particular, the present invention relates to a liquid crystal display such as an IPS liquid crystal display (In-plane Switching LCD) filled with a liquid crystal having positive dielectric anisotropy (Δε> 0). Useful for producing + C plates (positive C plates) used to improve the viewing angle characteristics of LCDs) and the viewing angle characteristics of circularly polarizing plates used as antireflection films for organic EL displays The present invention relates to a cured film forming composition, an alignment material, and a retardation material.

  IPS-LCD is characterized by little change in luminance / color due to viewing angle because no vertical tilt of liquid crystal molecules occurs, but the weak point is that it is difficult to increase the contrast ratio, luminance, and response speed. It is done. For example, as disclosed in Patent Document 1, a viewing angle compensation film is not used in an early IPS-LCD, and an IPS-LCD not using such a viewing angle compensation film has a tilt angle of Due to the relatively large light leakage in the dark state, there is a disadvantage of showing a low contrast ratio value.

Patent Document 2 discloses an IPS-LCD compensation film using a + C plate and a + A plate (positive A plate). This document shows the following configuration of the liquid crystal display element described therein.
1) A liquid crystal layer having a horizontal alignment is sandwiched between both substrates supplied by electrodes capable of applying an electric field parallel to the surface of the liquid crystal layer.
2) One or more + A plates and + C plates are sandwiched between both polarizing plates.
3) The main optical axis of the + A plate is perpendicular to the main optical axis of the liquid crystal layer.
4) of the liquid crystal layer retardation value R _LC, + C plate retardation value R _{+ C,} + A retardation value R _{+ A} plate is determined so as to satisfy the following equation.
R _LC : R _{+ C} : R _{+ A} ≒ 1: 0.5: 0.25
5) The relationship of the retardation value in the thickness direction of the protective film of the polarizing plate with respect to the retardation value of the + A plate and the + C plate is not shown (TAC, COP, PNB).

  Further, the + A plate is intended to provide an IPS-LCD having high contrast characteristics at the front and tilt angles and low color shift by minimizing light leakage in the dark state at the tilt angles. And an IPS-LCD having a + C plate is disclosed (Patent Document 3). Furthermore, in order to improve the viewing angle characteristics of a circularly polarizing plate used as an antireflection film for an organic EL display, a proposal has been made to use a + C plate (Patent Document 5).

JP-A-2-256603 JP 11-133408 A JP 2009-122715 A JP 2001-281669 A JP-A-2015-79256

  As previously proposed, the + C plate can compensate for light leakage where the viewing angle of the polarizing plate is large, so that a circular polarizing plate used as an antireflection film for IPS-LCDs and organic EL displays can be used. It is very useful as an optical compensation film. However, it is difficult to develop the vertical alignment (positive C plate) property by a conventionally known stretching method.

In addition, a conventionally proposed vertical alignment film using polyimide needs to use a polyimide solvent such as N-methyl-2-pyrrolidone for film production. For this reason, although it does not become a problem in a glass base material, when a base material is a film, there exists a problem of giving a damage to a base material at the time of alignment film formation. In addition, the vertical alignment film using polyimide requires firing at a high temperature, and there is a problem that the film substrate cannot withstand the high temperature.
Furthermore, a method for forming a vertical alignment film by directly treating a substrate with a silane coupling agent having a long-chain alkyl or the like has also been proposed, but when a hydroxy group does not exist on the substrate surface, There exists a problem that a process is difficult and a base material is restrict | limited (patent document 4).

  In recent years, in response to demands for reducing production costs, it has been demanded to produce by roll-to-roll on inexpensive resin films such as TAC (triacetyl cellulose) films and COP (cycloolefin polymer) films. However, it has been difficult to produce a + C plate on a resin film with an alignment film formed from a conventional material as described above.

  Accordingly, there is a need for an alignment material that has excellent adhesion and can form a highly reliable + C plate even on a resin film such as a TAC film, and a cured film forming composition for forming such an alignment material.

  The present invention has been made on the basis of the above findings and examination results, and the problem to be solved has excellent vertical alignment, and has transparency and solvent resistance required for an optical compensation film, Further, a cured film for providing an alignment material having an adhesive property with a base material and a polymerizable liquid crystal layer, and capable of stably aligning the polymerizable liquid crystal vertically on a resin film under low-temperature and short-time firing conditions. It is to provide a forming composition.

  Another object of the present invention is obtained from the above cured film-forming composition, and has excellent vertical alignment and adhesion, solvent resistance, and stable on low temperature and short time baking conditions even on a resin film. Another object of the present invention is to provide an alignment material capable of vertically aligning a polymerizable liquid crystal and a retardation material useful for a + C plate formed using the alignment material.

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

  In order to achieve the above object, the present inventors have made extensive studies and, as a result, select a cured film forming material based on a polymer having a vertically-alignable group and a polymerizable group containing a C═C double bond. Thus, it was found that a cured film having excellent vertical alignment and adhesion could be formed, and the present invention was completed.

（式［１］中、
Ｙ¹は単結合又は結合基を表し、
Ｙ²は単結合、炭素原子数１〜１５のアルキレン基若しくは−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−を表すか、又はベンゼン環、シクロヘキサン環若しくは複素環から選ばれる２価の環状基を表し、前記環状基上の任意の水素原子が、炭素原子数１〜３のアルキル基、炭素原子数１〜３のアルコキシル基、炭素原子数１〜３のフッ素含有アルキル基、炭素原子数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよく、
Ｙ³は単結合又は炭素原子数１〜１５のアルキレン基を表し、
Ｙ⁴は単結合を表すか、又はベンゼン環、シクロヘキサン環若しくは複素環から選ばれる２価の環状基、又は炭素原子数１７〜３０であってステロイド骨格を有する２価の有機基を表し、前記環状基上の任意の水素原子が、ヒドロキシ基、炭素原子数１〜３のアルキル基、炭素原子数１〜３のアルコキシル基、炭素原子数１〜３のフッ素含有アルキル基、炭素原子数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよく、
Ｙ⁵はベンゼン環、シクロヘキサン環又は複素環から選ばれる２価の環状基を表し、これらの環状基上の任意の水素原子が、ヒドロキシ基、炭素原子数１〜３のアルキル基、炭素原子数１〜３のアルコキシル基、炭素原子数１〜３のフッ素含有アルキル基、炭素原子数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよく、
ｎは０〜４の整数を表し、ｎが２以上の場合、Ｙ⁵同士は同一でも異なっていてもよく、
Ｙ⁶は水素原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のフッ素含有アルキル基、炭素原子数１〜１８のアルコキシル基又は炭素原子数１〜１８のフッ素含有アルコキシル基を表し、
Ｙ²及びＹ³におけるアルキレン基、並びに、前記環状基上の置換基及びＹ⁶におけるアルキル基、フッ素含有アルキル基、アルコキシル基及びフッ素含有アルコキシル基は、直鎖状、枝分かれ状、若しくは環状の何れか又はそれらの組み合わせであってもよく、
またＹ²及びＹ³におけるアルキレン基、並びに、Ｙ⁶におけるアルキル基、フッ素含有アルキル基、アルコキシル基及びフッ素含有アルコキシル基は、結合基同士が隣り合わない限り１ないし３の結合基で中断されていてもよく、
さらにＹ²、Ｙ⁴若しくはＹ⁵が２価の環状基を表すか、又はＹ⁴がステロイド骨格を有する２価の有機基を表すか、又はＹ²が−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−を表すか、又はＹ²若しくはＹ³がアルキレン基を表すか、又はＹ⁶がアルキル基若しくはフッ素含有アルキル基を表すとき、該２価の環状基、該ステロイド骨格を有する２価の有機基、該−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−、該アルキレン基、該アルキル基及び該フッ素含有アルキル基は、それらに隣接する基と結合基を介して結合していてもよく、
そして上記結合基は、−Ｏ−、−ＣＨ₂Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＮＨ−ＣＯ−Ｏ−及び−ＮＨ−ＣＯ−ＮＨ−からなる群から選ばれる基を表し、
但し、Ｙ²乃至Ｙ⁶がそれぞれ表すところの単結合、炭素原子数１〜１５のアルキレン基、ベンゼン環、シクロヘキサン環、複素環、ステロイド骨格を有する２価の有機基、−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のフッ素含有アルキル基、炭素原子数１〜１８のアルコキシル基及び炭素原子数１〜１８のフッ素含有アルコキシル基の炭素原子数の合計は６〜３０である）。That is, the present invention as a first aspect,
(A) a polymer having a vertical alignment group and a polymerizable group containing a C═C double bond, and (B) a cured film forming composition containing a radical polymerization initiator,
The vertical alignment group is a group represented by the following formula (1), and relates to a cured film forming composition.

(In Formula [1],
Y ¹ represents a single bond or a linking group,
Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or —CH ₂ —CH (OH) —CH ₂ —, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring. Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, 1 to 1 carbon atom 3 may be substituted with a fluorine-containing alkoxyl group or a fluorine atom,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton, Any hydrogen atom on the cyclic group is a hydroxy group, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or 1 to 1 carbon atom. 3 may be substituted with a fluorine-containing alkoxyl group or a fluorine atom,
Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is a hydroxy group, an alkyl group having 1 to 3 carbon atoms, or the number of carbon atoms. May be substituted with 1 to 3 alkoxyl groups, 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxyl groups, or fluorine atoms,
n represents an integer of 0 to 4, and when n is 2 or more, Y ⁵ may be the same or different,
Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Represent,
The alkylene group in Y ² and Y ³ , the substituent on the cyclic group, and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group in Y ⁶ are any of linear, branched, or cyclic Or a combination thereof,
In addition, the alkylene group in Y ² and Y ^3, and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group in Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. You can,
Furthermore, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents —CH ₂ —CH (OH) —CH. _2- , or when Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent organic group having the divalent cyclic group and the steroid skeleton The group, the —CH ₂ —CH (OH) —CH ₂ —, the alkylene group, the alkyl group and the fluorine-containing alkyl group may be bonded to a group adjacent thereto via a bonding group,
The linking group is a group selected from the group consisting of —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—. Represents
However, a single bond represented by Y ^{2 to} Y ^6, an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, —CH ₂ —CH ( OH) —CH ₂ —, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. The total number of carbon atoms is 6-30).

As a second aspect, in the polymer of component (A), the polymerizable group containing a C═C double bond is at least one selected from the group consisting of an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group. The present invention relates to a cured film forming composition described in the first aspect.
As a third aspect, (C) the cured film formation according to the first aspect or the second aspect, further containing at least one selected from the group consisting of a monomer having a polymerizable group containing a C═C double bond and a polymer Relates to the composition.
As 4th viewpoint, based on 100 mass parts of (A) component, 0.1 mass part-50 mass parts (B) component are contained, It is as described in any one among the 1st viewpoint thru | or 3rd viewpoint. The present invention relates to a cured film forming composition.
As a 5th viewpoint, based on 100 mass parts of (A) component, it is related with the cured film formation composition as described in a 3rd viewpoint or a 4th viewpoint containing 10 mass parts thru | or 1000 mass parts (C) component.

As a sixth aspect, the present invention relates to an alignment material obtained by curing the cured film forming composition according to any one of the first aspect to the fifth aspect.
As a seventh aspect, the present invention relates to a retardation material characterized by being formed using a cured film obtained from the cured film forming composition according to any one of the first aspect to the fifth aspect.

According to the first aspect of the present invention, in order to provide an alignment material that has excellent vertical alignment and can stably align a polymerizable liquid crystal vertically under low-temperature and short-time firing conditions even on a resin film. Useful cured film forming compositions can be provided.
According to the second aspect of the present invention, it is possible to provide an alignment material that has excellent vertical alignment and can stably align the polymerizable liquid crystal vertically under low-temperature and short-time firing conditions.
According to the 3rd aspect of this invention, it can form with high efficiency also on a resin film, and can provide the phase difference material which has high transparency, high solvent tolerance, and adhesiveness with a board | substrate and a liquid crystal film.

<Curing film forming composition>
The cured film forming composition of the present invention comprises (A) a polymer having a vertically-alignable group as a component and a polymerizable group containing a C = C double bond, and (B) a radical polymerization initiator as a component. contains. In addition to the components (A) and (B), the cured film forming composition of the present invention further comprises a group consisting of a monomer and a polymer having a polymerizable group containing a C═C double bond as the component (C). It can also contain at least one selected from And as long as the effect of this invention is not impaired, another additive can be contained.
Hereinafter, details of each component will be described.

<(A) component>
The component (A) contained in the cured film-forming composition of the present invention is a polymer having a vertical alignment group and a polymerizable group containing a C═C double bond.
In the present specification, the vertical alignment group represents, for example, a group containing a hydrocarbon group having about 6 to 30 carbon atoms, and specifically refers to a group represented by the formula [1] described later.
Accordingly, examples of the monomer having a vertical alignment group include a monomer having a hydrocarbon group having about 6 to 30 carbon atoms. Examples of the hydrocarbon group having 6 to 30 carbon atoms include linear, branched or cyclic alkyl groups having 6 to 30 carbon atoms or hydrocarbon groups having 6 to 30 carbon atoms including an aromatic group. . Accordingly, specific examples of the monomer containing a hydrocarbon group having 6 to 30 carbon atoms include alkyl ester of acrylic acid, alkyl ester of methacrylic acid, alkyl vinyl ether, 2-alkyl styrene, 3-alkyl styrene, 4-alkyl styrene, N-alkylmaleimide, wherein the alkyl group has 6 to 30 carbon atoms, or the alkyl group of these monomers includes the aromatic group having 6 to 30 carbon atoms as described above. The thing replaced by 30 hydrocarbon groups is mentioned.

式［１］中、Ｙ¹は単結合又は結合基を表す。
式［１］中、Ｙ²は単結合、炭素原子数１〜１５のアルキレン基又は−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−を表す。
またＹ²として、ベンゼン環、シクロヘキサン環または複素環から選ばれる２価の環状基が挙げられ、これら環状基上の任意の水素原子は、炭素原子数１〜３のアルキル基、炭素原子数１〜３のアルコキシル基、炭素原子数１〜３のフッ素含有アルキル基、炭素原子数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよい。More specifically, the vertical alignment group is a group represented by the following formula [1].

In formula [1], Y ¹ represents a single bond or a linking group.
In formula [1], Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms, or —CH ₂ —CH (OH) —CH ₂ —.
Y ^{2 includes a} divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring. An arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, or 1 carbon atom. Or an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.

  Examples of the heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like are more preferable. Is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benz It is an imidazole ring.

  Examples of the alkyl group listed as the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group, and the alkoxyl group includes oxygen as a group exemplified as a specific example of the alkyl group. A group to which an atom -O- is bonded can be exemplified. Examples of the fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group and alkoxyl group is substituted with a fluorine atom.

Among these, Y ² is preferably a single bond, an alkylene group having 1 to 15 carbon atoms, or a divalent cyclic group selected from a benzene ring or a cyclohexane ring, from the viewpoint of ease of synthesis. .

In the above formula [1], Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms.
In the above formula [1], Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is a hydroxy group, It is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. May be.

The alkyl group and the like mentioned as the heterocyclic ring and the substituent can be the same as those mentioned for Y ² above.

Furthermore, Y ⁴ may be a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton. Preferred examples thereof include cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estril, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, melatranyl, methyltestosteryl, noretisteryl, pregnenoyl, β-sitosteryl, It is a divalent group having a structure in which two hydrogen atoms are removed from a structure selected from stigmasteryl, testosteryl, acetic acid cholesterol ester, and the like. More specifically, for example, as follows.

Among these, Y ⁴ is a divalent cyclic group selected from a single bond, a benzene ring or a cyclohexane ring, or a divalent group having 17 to 30 carbon atoms and having a steroid skeleton from the viewpoint of ease of synthesis. The organic group is preferably.

In formula [1], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is a hydroxy group, having 1 to 3 carbon atoms. It may be substituted with an alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. The alkyl group and the like mentioned as the heterocyclic ring and the substituent can be the same as those mentioned above for Y ⁴ .

Among these, Y ⁵ is preferably a divalent cyclic group selected from a benzene ring or a cyclohexane ring.

In the formula [1], n represents an integer of 0 to 4, and when n is 2 or more, Y ⁵ may be the same group or different groups. Especially, n is preferably 0 to 3 from the viewpoint of availability of raw materials and ease of synthesis. More preferably, it is 0-2.

In formula [1], Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. Represents a fluorine-containing alkoxyl group.

Among them, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. Preferably there is. More preferably, Y ⁶ is an alkyl group having 1 to 17 carbon atoms or an alkoxyl group having 1 to 17 carbon atoms. Particularly preferably, Y ⁶ is an alkyl group having 1 to 16 carbon atoms or an alkoxyl group having 1 to 16 carbon atoms.

When Y ⁴ is a divalent organic group having a steroid skeleton, Y ⁶ is preferably a hydrogen atom.

  The alkylene group, alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxyl group mentioned in the definition in the above formula [1] are either linear, branched or cyclic, or a combination thereof. Also good.

  Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and 1-methyl-n-. Butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n -Propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n -Pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2, 3-dimethyl-n-butyl group, 3,3-di Til-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n- Pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl Group, 1-methyl-1-ethyl-n-butyl group, 1-methyl Ru-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n -Hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1- Ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group 1-methyl-3-ethyl-n-pentyl group, 2-methyl-2 -Ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n -Dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, etc. are mentioned.

As said alkylene group, the bivalent group which removed one arbitrary hydrogen atom from the said alkyl group can be mentioned.
Examples of the alkoxyl group include groups in which an oxygen atom —O— is bonded to the groups listed as specific examples of the alkyl group.
Examples of the fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group and alkoxyl group is substituted with a fluorine atom.

The alkylene group in Y ² and Y ³ , the substituent on the cyclic group, and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group in Y ⁶ are linear, branched, or cyclic. Any or a combination thereof may be used.

In addition, the alkylene group in Y ² and Y ^3, and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group in Y ⁶ are interrupted with 1 to 3 bonding groups unless the bonding groups are adjacent to each other. It may be.

Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents —CH ₂ —CH (OH) —. CH ₂ —, or when Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group and the divalent group having the steroid skeleton The organic group, the —CH ₂ —CH (OH) —CH ₂ —, the alkylene group, the alkyl group, and the fluorine-containing alkyl group may be bonded to a group adjacent thereto via a bonding group.

In addition, the linking group includes —O—, —CH ₂ O—, —CO—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—CO—O—, —O—CO—NH. Represents a group selected from the group consisting of — and —NH—CO—NH—.

Note that a single bond represented by Y ^{2 to} Y ^6, an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, —CH ₂ —CH ( OH) —CH ₂ —, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. The total number of carbon atoms is 6-30, for example, 6-20.
Among these, in consideration of vertical alignment and applicability of the polymerizable liquid crystal, the vertical alignment group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 16 carbon atoms.

  In the polymer of component (A), examples of the polymerizable group containing a C═C double bond include an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.

The polymerizable group containing a C═C double bond can be incorporated into the side chain of the main skeleton of the polymer, that is, as a specific side chain having a polymerizable group containing a C═C double bond, It can be incorporated into the side chain of the polymer.
In the polymer of the component (A), the specific side chain having a polymerizable group containing a C═C double bond has 3 to 16 carbon atoms and has an unsaturated bond at the terminal. The specific side chain represented by the formula (b2) is particularly preferable.

式（ｂ２）中、Ｒ⁵¹は、炭素原子数が１〜１４であり、脂肪族基、環式構造を含む脂肪族基および芳香族基よりなる群から選ばれる２価の有機基、または、この群から選ばれる複数の２価の有機基の組み合わせからなる２価の有機基である。Ｒ⁵¹は、エステル結合、エーテル結合、アミド結合、−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−結合またはウレタン結合などを含んでいてもよい。
式（ｂ２）において、Ｒ⁵²は水素原子またはメチル基であり、Ｒ⁵²が水素原子である特定側鎖が好ましく、より好ましくは、末端がアクリロイル基、メタクリロイル基またはスチリル基である特定側鎖である。

In formula (b2), R ⁵¹ has 1 to 14 carbon atoms and is a divalent organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or A divalent organic group comprising a combination of a plurality of divalent organic groups selected from this group. R ⁵¹ may contain an ester bond, an ether bond, an amide bond, a —CH ₂ CH (OH) CH ₂ — bond, a urethane bond, or the like.
In the formula (b2), R ⁵² is a hydrogen atom or a methyl group, and a specific side chain in which R ⁵² is a hydrogen atom is preferred, and more preferably a specific side chain in which the terminal is an acryloyl group, a methacryloyl group or a styryl group. is there.

  The method for obtaining the polymer of component (A) of the present invention is not particularly limited. For example, a polymer having a vertical alignment group and a specific functional group is generated in advance by a polymerization method such as radical polymerization. Next, by reacting a compound having a group that reacts with the specific functional group and a polymerizable group containing a C═C double bond (hereinafter referred to as a specific compound), a polymer of component (A) can be obtained. it can.

  As other methods, for a polymer having a specific functional group, a compound having a group that reacts with the specific functional group and a compound having a vertical alignment group, a group that reacts with the specific functional group, and a C = C double bond. By reacting a compound having a functional group, the polymer of component (A) can be obtained.

  Here, the specific functional group means a functional group such as a carboxyl group, an epoxy group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types of functional groups selected from these functional groups. .

  In the reaction with the specific functional group described above, the preferred combination of the specific functional group and the functional group of the specific compound that is involved in the reaction is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, or a phenolic hydroxy group. Group and epoxy group, carboxyl group and isocyanate group, amino group and isocyanate group, or hydroxy group and acid chloride.

  Moreover, the method of obtaining the polymer which has a specific functional group is not specifically limited. As an example, a monomer having a functional group (specific functional group) for reacting with a specific compound, that is, a carboxyl group, an epoxy group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group, an isocyanate group, or the like. It can be obtained by polymerizing a monomer (also referred to as a specific monomer). Here, the monomer having the specific functional group used for the polymerization may be used alone, or a plurality of types may be used in combination as long as the combination does not react during the polymerization.

  Hereinafter, specific examples of the monomer necessary for obtaining the polymer having the specific functional group, that is, the specific monomer will be described. However, it is not limited to these.

  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 and N- (carboxyphenyl) acrylamide.

  Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2- And epoxy-5-hexene and 1,7-octadiene monoepoxide.

  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, 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 (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Shi-6-hydroxy-norbornene-2-carboxylic-6-lactone and 5-methacryloyloxy such acryloyloxy-6-hydroxy-norbornene-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 and N- (hydroxyphenyl) maleimide.

  As a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.

In the present invention, when a polymer having a specific functional group is obtained, in addition to the specific monomer, a monomer that can be copolymerized with the monomer and does not have the specific functional group can be used in combination.
Specific examples of such monomers include acrylic ester compounds or methacrylic ester compounds having a structure different from that of the specific monomer, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds. .

Hereinafter, although the specific example of the said monomer is given, it is not limited to these.
Examples of the acrylate compound having a structure different from that of the specific monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, and naphthyl acrylate. , Anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl Acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and the like 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound having a structure different from that of the specific monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, and naphthyl methacrylate. , Anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, Tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate Acrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, etc. Can be mentioned.

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

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

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

Moreover, the polymer which has the said specific functional group can use a commercial item suitably.
Specific examples of commercially available polymers having one or more epoxy groups in the side chain or terminal include bisphenol A type epoxy resins such as jER1001, 1002, 1003, 1004, 1055, 1007, 1009, 1010, 834, 828 (Mitsubishi Chemical Co., Ltd.), etc., and bisphenol F type epoxy resin, jER806, 807 (Mitsubishi Chemical Co., Ltd.), etc. are phenol novolac type epoxy. As the resin, jER152, 154 (above, manufactured by Mitsubishi Chemical Corporation), EPPN201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.) and the like, and as the cresol novolac type epoxy resin, ECN-1299 (Asahi Kasei). EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020 EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), jER80S75 (manufactured by Mitsubishi Chemical Co., Ltd.), etc. As the 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of polyol, EHPE-3150 (manufactured by Daicel Corporation) and the like can be mentioned.

  As specific examples of commercially available polymers having one or more hydroxy groups in the side chain or terminal, specific examples of polyether polyols include ADEKA Adeka Polyether P Series, G Series, EDP Series, BPX Series, FC Series, CM series, NOF UNIOX (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, UNIOR (registered trademark) TG-330, TG-1000, TG -3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, Nonion (registered trademark) LT-221, ST-221, OT-221, etc. Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355 OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD- X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD-X-2560, Kuraray polyols 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, C -590, C-1050, C-2050, C-2090, C-3090, etc., as specific examples of polycaprolactone polyol, DIC polylite (registered trademark) OD- -2155, OD-X-640, OD-X-2568, Daicel Chemical Plaxel (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312 320 or the like.

The polymer of component (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 150,000, and more preferably 3,000 to 100,000. Even more preferred. If the weight average molecular weight is over 200,000, the solubility in the solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 1,000, the light There may be insufficient curing during curing and solvent resistance and heat resistance may decrease.
In the present specification, the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

  In the polymer of component (A), the proportion of the vertically aligning group is preferably 3 mol% to 50 mol% per 100 mol of all repeating units of the polymer, and preferably 5 mol% to 45 mol%. Is more preferable. When the amount is less than 3 mol%, the vertical alignment may be insufficient, and when it is more than 50 mol%, the adhesion to the liquid crystal may be adversely affected.

  In the polymer of component (A), the proportion of the polymerizable group containing a C═C double bond is preferably 20 mol% to 97 mol% per 100 mol of all repeating units of the polymer, and 25 mol%. More preferably, it is -95 mol%. When it is less than 20 mol%, curing may be insufficient, and when it is more than 97 mol%, vertical alignment may be insufficient.

<(B) component>
The component (B) in the cured film forming composition of the present invention is a radical polymerization initiator.
As the radical polymerization initiator, known ones can be used. For example, alkylphenones, benzophenones, acylphosphine oxides, Michler's benzoylbenzoates, oxime esters, tetramethylthiuram monosulfides, Examples include thioxanthones.

Examples of radical polymerization initiators used in the present invention include α-diketones such as diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; thioxanthone, 2, Benzophenones such as 4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethylaminoacetophenone, α , Α-dimethoxy-α-acetoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 1- [2-methyl-4-methylthiophenyl] -2-morpholine Acetophenones such as no-1-propanone, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; anthraquinone Quinones such as 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine; [1,2′-bisimidazole] -3,3 ′, Bisimidazoles such as 4,4′-tetraphenyl, [1,2′-bisimidazole] -1,2′-dichlorophenyl-3,3 ′, 4,4′-tetraphenyl, di-tert-butyl peroxide Peroxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide And acylphosphine oxides.
Commercially available products include Irgacure 184, 369, 379EG, 651, 500, 907, CGI369, CG24-61, OXE02, Lucirin LR8728, Lucirin TPO, Darocur 1116, 1173 (above, manufactured by BASF Corporation), Ubekrill P36 (UCB) (Commercially available) and the like can be listed.

  Among the above, 1- [2-methyl-4-methylthiophenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Acetophenones such as α, α-dimethoxy-α-phenylacetophenone, phenacyl chloride, tribromomethylphenyl sulfone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2′-bisimidazoles and 4, Combination of 4′-bis (diethylamino) benzophenone and mercaptobenzothiazole, Lucillin TPO (trade name), Irgacure 651 (trade name), Irgacure 369 (trade name), Irgacure 907 (trade name), Irgacure OXE02 (trade name) Is preferred.

The radical polymerization initiators may be used alone or in combination of two or more.
The radical polymerization initiator is preferably used in an amount of 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 30 parts by mass with respect to 100 parts by mass of the component (A). Can do. If the amount of radical polymerization initiator used is less than the above range, it is easily affected by radical deactivation by oxygen (decrease in sensitivity), and if it exceeds the above range, compatibility is deteriorated and storage stability is lowered. There is a tendency to do.

<(C) component>
The cured film forming composition of this invention may contain at least 1 type chosen from the group which consists of the monomer and polymer which have a polymeric group containing a C = C double bond as (C) component.

In the present specification, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid. Further, (meth) acryloyl group, a CH ₂ = CHCO-, represents the CH (CH ₃₎ = CHCO-.

  Hereinafter, as the monomer and polymer having a polymerizable group containing a C = C double bond of the component (C) of the present invention, from the viewpoint of increasing the film strength, a polymerizable group containing a C = C double bond is contained in one molecule. Monomers and polymers having two or more in each are preferred. Hereinafter, although an example of a suitable compound is given, (C) component is not limited to these illustrations.

Examples of the compound having two (meth) acryloyl groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, Pentaerythritol di (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyl Oxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, trishydroxyethyl isocyanurate di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] Fluorene, undecylenoxyethylene glycol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, etc. Cited The

  The compound which has 2 or more of (meth) acryloyl groups can use a commercial item suitably, for example, light acrylate 3EG-A, light acrylate 4EG-A, light acrylate 9EG-A, light acrylate 14EG-A, light acrylate PTMGA -250, light acrylate NP-A, light acrylate MPD-A, light acrylate 1.6HX-A, light acrylate 1.9ND-A, light acrylate MOD-A, light acrylate DCP-A, light acrylate BP-4EAL, light Acrylate BP-4PA, Light acrylate HPP-A, Light ester G-201P, Light ester P-2M, Light ester EG, Light ester 2EG, Light ester 3EG, Light ester 4EG, Light Steal 9EG, light ester 14EG, light ester 1.4BG, light ester NP, light ester 1.6HX, light ester 1.9ND, light ester G-101P, light ester G-201P, light ester BP-2EMK [above, any NK Ester 701A, A-200, A-400, A-600, A-1000, A-B1206PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD- N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, DCP, DCP- N, the same HD-N, the same NOD-N, the same NPG, the same 1206 PE, the same 701, the same 9 PG [all are manufactured by Shin-Nakamura Chemical Co., Ltd.]; FANCYL FA-124AS, the same FA-129AS, the same FA -222A, FA-240A, FA-P240A, FA-P270A, FA-321A, FA-324A, FA-PTG9A, FA-121M, FA-124M, FA-125M, FA -220M, FA-240M, FA-320M, FA-321M, FA-3218M, FA-PTG9M [All above, Hitachi Chemical Co., Ltd. DPGDA, HODA, TPGDA, EBECRYL (registered trademark) 145, 150, IRR214-K, PEG400DA-D, EBECRYL (registered trademark) 11, HPDNA [manufactured by Daicel Ornex Co., Ltd.]; Biscote # 195, # 230, the same # 260, the same # 310HP, the same # 335HP, the same # 700HV, the same # 540, the same # 802, the same # 295 [all are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.].

  Examples of the compound having three (meth) acryloyl groups (trifunctional compound) include, for example, ethylene oxide-modified 1,1,1-trimethylolethane tri (meth) acrylate [ethylene oxide addition mole number 3 to 30], ethylene oxide-modified trimethylol. Propane tri (meth) acrylate [ethylene oxide addition mole number 3-30], propylene oxide modified trimethylolpropane tri (meth) acrylate [propylene oxide addition mole number 3-30], ethylene oxide modified glycerin tri (meth) acrylate [ethylene oxide addition mole] 3-30], propylene oxide-modified glycerin tri (meth) acrylate [propylene oxide addition mole number 3-30], tris (2- (acryloyloxy) ethyl) isocyanurate, ε-cap Lactone-modified tris (2- (acryloyloxy) ethyl) isocyanurate [ε-caprolactone addition mole number 1-30], 1,1,1-trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Examples include ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and glycerin tri (meth) acrylate.

  Commercially available products can be suitably used as the trifunctional compound, for example, Biscote # 360 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); NK ester A-GLY-9E, A-GLY-20E, AT-20E [above or more] , All manufactured by Shin-Nakamura Chemical Co., Ltd.]; TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [above, both manufactured by Daicel Ornex Co., Ltd.], Biscoat # 295, # 300 [above, both of Osaka Organic Chemical Industry Co., Ltd.]; Light Acrylate TMP-A, PE-3A, Light Ester TMP [All above, manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9300, A-9300-1CL, A-TMM-3, same A-TMM-3L, same A-TMM-3LM-N, same A-TMPT, same TMPT [all are made by Shin-Nakamura Chemical Co., Ltd.]; P TIA, PETRA, TMPTA, EBECRYL (R) 180 [or, both Daicel Orunekusu Ltd.] and the like.

  Examples of the compound having four (meth) acryloyl groups (tetrafunctional compound) include, for example, ethylene oxide-modified ditrimethylolpropane tetra (meth) acrylate [ethylene oxide addition mole number 4 to 40], ethylene oxide-modified pentaerythritol tetra (meth) acrylate [ Ethylene oxide addition mole number 4 to 40], ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like.

  Commercially available products can be suitably used as the tetrafunctional compound, for example, NK ester ATM-4E, ATM-35E [all are manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 40 [Daicel Ornex] Biscoat # 300 [Osaka Organic Chemical Co., Ltd.]; light acrylate PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK ester AD-TMP, A-TMMT [all above. Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 140, 1142, and 180 [all are manufactured by Daicel Ornex Co., Ltd.].

  Examples of the compound having 5 or more (meth) acryloyl groups (a compound having 5 or more functional groups) include ethylene oxide-modified dipentaerythritol hexa (meth) acrylate [ethylene oxide addition mole number 6 to 60], ethylene oxide-modified tripentaerythritol octa ( And (meth) acrylate [additional mole number of ethylene oxide 6 to 60], dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate and the like.

  Commercially available products can be suitably used as the above five or more functional compounds. For example, NK ester A-DPH-12E [manufactured by Shin-Nakamura Chemical Co., Ltd.], Biscoat # 802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Acrylate DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9550, A-DPH [all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; Can be mentioned.

  Examples of the bifunctional urethane (meth) acrylate include urethanized product of phenylglycidyl ether (meth) acrylic acid adduct and hexamethylene diisocyanate, phenylglycidyl ether (meth) acrylic acid adduct and toluene diisocyanate. Etc.

  Commercially available products can be suitably used as the bifunctional urethane (meth) acrylate, for example, AH-600, AT-600 [all are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-2PPA, U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-W2A [all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 210 215, 230, 244, 245, 270, 280 / 15IB, 284, 285, 4858, 8307, 8402, 8411, 8804, 8807, 9227EA, 9270 , KRM (registered trademark) 7735 [above, both manufactured by Daicel Ornex Co., Ltd.]; Murasaki (registered trademark) UV-6630B, 7000B 7461TE, 2000B, 2750B, 3000, 3200B, 3210EA, 3300B, 3310B, 3500BA, 3520TL, 3700B, 6640B [all are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.], etc. Is mentioned.

  Specific examples of commercially available polyfunctional urethane (meth) acrylate compounds having three (meth) acryloyl groups include NK Oligo UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) 204, 205, 264, 265, 294 / 25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (Registered Trademark) 8296, 8667 [above, Daicel Ornex Co., Ltd. )]; Murasaki (registered trademark) UV-7550B, 7000B, 7510B, 7461TE, 2750B [all are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.].

  Specific examples of commercially available polyfunctional urethane (meth) acrylate compounds having four (meth) acryloyl groups include EBECRYL (Registered Trademark) 8210, 8405, KRM (Registered Trademark) 8528 [above, both are Daicel Ornex Manufactured by Co., Ltd.]; Shikko (registered trademark) UV-7650B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd.].

  Examples of the polyfunctional urethane (meth) acrylate compound having 5 or more (meth) acryloyl groups (pentafunctional or more urethane (meth) acrylate) are urethanized products of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate, Urethanes of pentaerythritol tri (meth) acrylate and toluene diisocyanate, urethanates of pentaerythritol tri (meth) acrylate and isophorone diisocyanate, urethanates of dipentaerythritol penta (meth) acrylate and hexamethylene diisocyanate, etc. .

  Commercially available urethane (meth) acrylate having 5 or more functional groups can be suitably used. For example, UA-306H, UA-306T, UA-306I, UA-510H [above, all are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA-33H [above, all manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (Registered Trademark) 220, 1290, 5129, 8254, 8301R, KRM (Registered Trademark) 8200, 8200AE, 8904, 8452 [all are manufactured by Daicel Ornex Co., Ltd.]; Trademarks) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B [above, both Nippon Synthetic Chemical Industry Co., Ltd.], and the like.

  The component (C) of the present invention may be a polymer compound having one or more side chains whose terminals are polymerizable unsaturated bonds in the molecule. As such a polymer compound having a side chain whose terminal is a polymerizable unsaturated bond, a polymer compound having a (meth) acryloyl group in two or more side chains in the molecule is preferable.

  Examples of the polymer compound include polymer compounds containing one or more (meth) acryloyl groups such as urethane acrylic, epoxy acrylic, and various (meth) acrylates.

  The weight average molecular weight of the polymer compound (C) is preferably 1,000 to 200,000, more preferably 5,000 to 50,000. If the molecular weight is less than 1,000, the effects of the present invention may not be achieved. On the other hand, if the molecular weight exceeds 100,000, it may not dissolve in the composition.

  Examples of such a compound as component (C) include Acryt 8BR-930M, 8UH-1006, 8KQ-2001, 8KX-078, 1SX-1055 [more, manufactured by Taisei Fine Chemical Co., Ltd.], SMP -250A, SMP-360A, SMP-550A [above, manufactured by Kyoeisha Chemical Co., Ltd.].

  (C) Content in the case of containing a component is 10 mass parts thru | or 1000 mass parts based on 100 mass parts of (A) component, Preferably, it is 15 mass parts thru | or 500 mass parts.

<Solvent>
The cured film forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used in that case is only required to be able to dissolve the component (A), the component (B), the component (C) and / or other additives as described below, and the type and structure thereof are particularly limited. Not.

  Specific examples of the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, Toluene, xylene, methyl Tyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Is mentioned.

  When the cured film forming composition of the present invention is used to produce an alignment material by forming a cured film on a resin film, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable from the viewpoint that the resin film is a resistant solvent.

  These solvents can be used singly or in combination of two or more.

<Other additives>
Furthermore, the cured film forming composition of the present invention is a sensitizer, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, as necessary, as long as the effects of the present invention are not impaired. Dyes, storage stabilizers, antifoaming agents, antioxidants and the like can be contained.

<Preparation of cured film forming composition>
The cured film forming composition of the present invention contains (A) a polymer having a vertical alignment group as a component and a polymerizable group containing a C = C double bond, and (B) a polymerization initiator as desired. Component (C) may contain at least one selected from the group consisting of monomers and polymers having a polymerizable group containing a C═C double bond, and other additives as long as the effects of the present invention are not impaired. Composition. Usually, they are used in the form of a solution in which they are dissolved in a solvent.

Preferred examples of the cured film forming composition of the present invention are as follows.
[1]: A cured film forming composition containing 0.1 part by mass to 50 parts by mass of component (B) based on 100 parts by mass of component (A) and component (A).
[2]: Based on (A) component, 100 parts by weight of component (A), 0.1 to 50 parts by weight of component (B), based on 100 parts by weight of component (A), 10 parts by weight A cured film forming composition containing 1000 parts by mass of component (C) and a solvent.

The blending ratio, preparation method, etc. when the cured film forming composition of the present invention is used as a solution are described in detail below.
The ratio 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 60% by mass, preferably 2%. It is from mass% to 50 mass%, and more preferably from 2 mass% to 20 mass%. Here, solid content means what remove | excluded the solvent from all the components of the cured film formation composition.

  The preparation method of the cured film forming composition of this invention is not specifically limited. As a preparation method, for example, a method of mixing the component (B), further the component (C), etc. in a predetermined ratio with a solution of the component (A) dissolved in a solvent to obtain a uniform solution, or this preparation method In an appropriate stage, there may be mentioned a method in which other additives are further added and mixed as necessary.

  The prepared cured film-forming composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Hardened film, alignment material and retardation material>
A solution of the cured film forming composition of the present invention 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, or chromium, a glass substrate, a quartz substrate, or ITO. Substrates) and film substrates (eg, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene) On a resin film such as a film, etc., a bar coating, spin coating, flow coating, roll coating, slit coating, spin coating following slits, ink jet coating, printing, etc. to form a coating film, Relieved Dried by heating with a plate or an oven or the like, it is possible to form a cured film. The cured film can be used as an alignment material as it is.

  The heating and drying conditions may be such that the crosslinking reaction with the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) do not elute into the polymerizable liquid crystal solution applied thereon. A heating temperature and a heating time appropriately selected from the range of 200 ° C. and a time of 0.4 minutes to 60 minutes are adopted. The heating temperature and the heating time are preferably 70 to 160 ° C. and 0.5 to 10 minutes.

  The film thickness of the cured film (alignment material) formed using the curable composition of the present invention is, for example, 0.05 μm to 5 μm, and is appropriately determined in consideration of the level difference of the substrate used and optical and electrical properties. You can choose.

  Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a phase difference material such as a polymerizable liquid crystal solution having vertical alignment property is applied onto the alignment material. Can be oriented on the orientation material. And the phase difference material can be formed as a layer which has optical anisotropy by hardening the phase difference material which became the orientation state as it is. And when the board | substrate which forms an orientation material is a film, it becomes useful as a phase difference film.

In addition, after using the two substrates having the alignment material of the present invention formed as described above, the alignment materials on both substrates are bonded to each other via a spacer, and then between the substrates. A liquid crystal display element in which liquid crystal is injected to align the liquid crystal may be used.
Thus, the cured film forming composition of this invention can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.

EXAMPLES 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.
[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.

<A component ingredient>
LAA: lauryl acrylate PAA: palmityl acrylate HEMA: 2-hydroxyethyl methacrylate GMA: glycidyl methacrylate AOI: Karenz AOI manufactured by Showa Denko K.K.
AIBN: α, α′-azobisisobutyronitrile LA: lauric acid M100: 3,4-epoxycyclohexylmethyl methacrylate 5PCA: 4- (4-pentylcyclohexyl) benzoic acid

<B component>
IRG: IRSFACURE 907 manufactured by BASF
OXE: IRGACURE OXE 02 manufactured by BASF

<C component>
DPHA: manufactured by Daicel Ornex Co., Ltd. dipentaerythritol hexaacrylate SMP: manufactured by Kyoeisha Chemical Co., Ltd. UV curable acrylic polymer SMP-550A

<Others>
MAA: CYM303 methacrylate: hexamethoxymethylmelamine PTSA: p-toluenesulfonic acid monohydrate

<Solvent>
Each cured film forming composition of an Example and a comparative example contained a solvent, and propylene glycol monomethyl ether (PM), butyl acetate (BA), and ethyl acetate (EA) were used as the solvent.

<Measurement of molecular weight of polymer>
The molecular weight of the acrylic copolymer in the polymerization example is as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co. And measured.
The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L)
Flow rate: 1.0 mL / minute standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories ( Molecular weight about 12,000, 4,000, 1,000).

<Polymerization Example 1>
Acrylic copolymer solution was obtained by dissolving 3.0 g of LAA, 12.0 g of GMA and 0.3 g of AIBN as a polymerization catalyst in 45.7 g of PM and reacting at 80 ° C. for 20 hours. The obtained acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (P1). Mn of the obtained acrylic copolymer was 14,000 and Mw was 38,000.

<Polymerization example 2>
3.0 g of PAA, 12.0 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The obtained acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (P2). Mn of the obtained acrylic copolymer was 12,000 and Mw was 30,000.

<Polymerization Example 3>
Acrylic copolymer solution was obtained by dissolving 3.0 g of LAA, 12.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 45.7 g of PM and reacting at 80 ° C. for 20 hours. The obtained acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (P3). Mn of the obtained acrylic copolymer was 8,600 and Mw was 20,000.

<Polymerization example 4>
An acrylic copolymer solution was obtained by dissolving 1.5 g of LAA, 13.5 g of GMA and 0.3 g of AIBN as a polymerization catalyst in 45.7 g of PM and reacting at 80 ° C. for 20 hours. The obtained acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (P4). Mn of the obtained acrylic copolymer was 15,000 and Mw was 32,000.

<Polymerization example 5>
4.5 g of LAA, 10.5 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The obtained acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (P5). Mn of the obtained acrylic copolymer was 14,000 and Mw was 31,000.

<Polymerization Example 6>
10.0 g of M100 and 0.4 g of AIBN as a polymerization catalyst were dissolved in 46.4 g of PM and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The obtained acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (P6). Mn of the obtained acrylic copolymer was 18,000 and Mw was 38,000.

<Polymerization Example 7>
MAA (13.8 g), LAA (14.1 g), HEMA (7.2 g), AIBN (0.68 g) as a polymerization catalyst were dissolved in PM (107.0 g) and reacted at 80 ° C. for 16 hours to obtain an acrylic copolymer solution (solid content concentration). 25% by mass) (P7) was obtained. Mn of the obtained acrylic copolymer was 13,300 and Mw was 27,800.

<Synthesis Example 1>
7.5 g of the acrylic copolymer (P1) obtained in Polymerization Example 1, 4.5 g of acrylic acid, 0.4 g of dibutylhydroxytoluene, 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 30 g of PM, and 20 ° C. at 110 ° C. Reacted for hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-1) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PA-1) had an acroyl group.

<Synthesis Example 2>
7.5 g of the acrylic copolymer (P2) obtained in Polymerization Example 2, 4.5 g of acrylic acid, 0.4 g of dibutylhydroxytoluene, 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 30 g of PM, and 20 ° C. at 110 ° C. Reacted for hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-2) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PA-2) had an acroyl group.

<Synthesis Example 3>
2.0 g of the acrylic copolymer (P3) obtained in Polymerization Example 3, 4.3 g of 2-acryloyloxyethyl isocyanate, 0.4 g of dibutylhydroxytoluene, 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran, and 60 ° C. For 5 hours. The solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-3) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PA-3) had an acroyl group.

<Synthesis Example 4>
6.8 g of the acrylic copolymer (P4) obtained in Polymerization Example 4, 4.5 g of acrylic acid, 0.4 g of dibutylhydroxytoluene, 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 30 g of PM, and 20 ° C. at 110 ° C. Reacted for hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-4) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PA-4) had an acroyl group.

<Synthesis Example 5>
8.2 g of acrylic copolymer (P5) obtained in Polymerization Example 5, 4.5 g of acrylic acid, 0.4 g of dibutylhydroxytoluene, 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 30 g of PM, and 20 ° C. at 110 ° C. Reacted for hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-5) having an acroyl group. ¹ H-NMR analysis was performed to confirm that the acrylic copolymer (PA-5) had an acroyl group.

<Synthesis Example 6>
8.0 g of the acrylic copolymer (P6) obtained in Polymerization Example 6, 2.4 g of acrylic acid, 1.6 g of LA, 0.4 g of dibutylhydroxytoluene, 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 50 g of PM, The reaction was carried out at 110 ° C. for 20 hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-6) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PA-6) had an acroyl group.

<Synthesis Example 7>
8.0 g of acrylic copolymer (P6) obtained in Polymerization Example 6, 1.8 g of acrylic acid, 1.7 g of LA, 0.4 g of dibutylhydroxytoluene, 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 50 g of PM, The reaction was carried out at 110 ° C. for 20 hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-7) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PA-7) had an acroyl group.

<Synthesis Example 8>
8.0 g of acrylic copolymer (P6) obtained in Polymerization Example 6, 3.2 g of acrylic acid, 2.2 g of 5PCA, 0.4 g of dibutylhydroxytoluene, 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM, The reaction was carried out at 110 ° C. for 20 hours. The solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-8) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PA-8) had an acroyl group.

<Example>
Each cured film forming composition of an Example was prepared with the composition shown in Table 1. Next, a cured film was formed using each cured film forming composition, and vertical alignment and adhesion were evaluated for each of the obtained cured films.

<Comparative example>
With reference to the method described in WO2015 / 019962, each cured film forming composition of Comparative Example shown in Table 2 was prepared. Next, a cured film was formed using each cured film forming composition, and vertical alignment and adhesion were evaluated for each of the obtained cured films.

[Evaluation of vertical alignment]
Each cured film forming composition of an Example was apply | coated with the wet film thickness of 4 micrometers on the TAC film using the bar coater. Heat drying was performed in a heat circulation oven at a temperature of 110 ° C. for 60 seconds, and then the coating film was exposed at 1000 mJ / cm ² to form a cured film on the TAC film.
On this cured film, a polymerizable liquid crystal solution RMS03-015 for vertical alignment manufactured by Merck Co., Ltd. was applied with a wet film thickness of 6 μm using a bar coater. This coating film was exposed at 500 mJ / cm ² to prepare a retardation material.
With respect to these prepared retardation materials, the incidence angle dependence of the in-plane retardation was measured using a phase difference measuring apparatus RETS100 manufactured by Otsuka Electronics Co., Ltd. Those having an in-plane retardation value of 0 at an incident angle of 0 ° and an in-plane retardation of 38 ± 5 nm at an incident angle of ± 50 ° were judged to be vertically oriented. The evaluation results are summarized in Table 3 later.

Each cured film forming composition of the comparative example was applied on a TAC film with a wet film thickness of 4 μm using a bar coater. Each was heated and dried in a heat circulation oven at a temperature of 110 ° C. for 60 seconds to form a cured film on the TAC film.
On this cured film, a polymerizable liquid crystal solution RMS03-015 for vertical alignment manufactured by Merck Co., Ltd. was applied with a wet film thickness of 6 μm using a bar coater. This coating film was exposed at 500 mJ / cm ² to prepare a retardation material.
With respect to these prepared retardation materials, the incidence angle dependence of the in-plane retardation was measured using a phase difference measuring apparatus RETS100 manufactured by Otsuka Electronics Co., Ltd. Those having an in-plane retardation value of 0 at an incident angle of 0 ° and an in-plane retardation of 38 ± 5 nm at an incident angle of ± 50 ° were judged to be vertically oriented. The evaluation results are summarized in Table 3 later.

[Evaluation of adhesion]
Each cured film formation composition of an Example and a comparative example was apply | coated with the wet film thickness of 4 micrometers on the TAC film using the bar coater. Heat drying was performed in a heat circulation oven at a temperature of 110 ° C. for 60 seconds, and then the coating film was exposed at 1000 mJ / cm ² to form a cured film on the TAC film.
On this cured film, a polymerizable liquid crystal solution RMS03-015 for vertical alignment manufactured by Merck Co., Ltd. was applied with a wet film thickness of 6 μm using a bar coater. The coating film on this substrate was exposed at 500 mJ / cm ² to produce a retardation material.
This phase difference material was cut with a cutter knife so as to be 5 × 5 squares at intervals of 1 mm in length and width. A cellophane tape peeling test was performed on the cut using a scotch tape. In the evaluation, a case where all the 25 squares were not peeled off was marked with ◯, and a case where even one square was peeled off was marked with x. The evaluation results are summarized in Table 3 later.

  As shown in Table 3, the alignment material obtained using the cured film-forming composition of the example had good vertical alignment properties similar to the alignment material obtained using the cured film-forming composition of the comparative example. showed that.

  The cured films obtained using the cured film forming compositions of the examples showed excellent adhesion. On the other hand, it was difficult for the cured film obtained using the cured film forming composition of the comparative example to obtain adhesion.

  The cured film forming composition according to the present invention is very useful as a material for forming a liquid crystal alignment film of a liquid crystal display element and an alignment material for forming an optically anisotropic film provided inside or outside the liquid crystal display element. In particular, it is suitable as a material for an optical compensation film of a circularly polarizing plate used as an antireflection film for an IPS-LCD or an organic EL display.

Claims (7)

(A) a polymer having a vertical alignment group and a polymerizable group containing a C═C double bond, and (B) a cured film forming composition containing a radical polymerization initiator,
The said vertical alignment group is group represented by following formula (1), The cured film formation composition characterized by the above-mentioned.

(In Formula [1],
Y ¹ represents a single bond or a linking group,
Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or —CH ₂ —CH (OH) —CH ₂ —, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring. Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, 1 to 1 carbon atom 3 may be substituted with a fluorine-containing alkoxyl group or a fluorine atom,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton, Any hydrogen atom on the cyclic group is a hydroxy group, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or 1 to 1 carbon atom. 3 may be substituted with a fluorine-containing alkoxyl group or a fluorine atom,
Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is a hydroxy group, an alkyl group having 1 to 3 carbon atoms, or the number of carbon atoms. May be substituted with 1 to 3 alkoxyl groups, 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxyl groups, or fluorine atoms,
n represents an integer of 0 to 4, and when n is 2 or more, Y ⁵ may be the same or different,
Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. Represent,
The alkylene group in Y ² and Y ³ , the substituent on the cyclic group, and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group in Y ⁶ are any of linear, branched, or cyclic Or a combination thereof,
In addition, the alkylene group in Y ² and Y ^3, and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group in Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. You can,
Furthermore, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents —CH ₂ —CH (OH) —CH. _2- , or when Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent organic group having the divalent cyclic group and the steroid skeleton The group, the —CH ₂ —CH (OH) —CH ₂ —, the alkylene group, the alkyl group and the fluorine-containing alkyl group may be bonded to a group adjacent thereto via a bonding group,
The linking group is a group selected from the group consisting of —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—. Represents
However, a single bond represented by Y ^{2 to} Y ^6, an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, —CH ₂ —CH ( OH) —CH ₂ —, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. The total number of carbon atoms is 6-30).   In the polymer of component (A), the polymerizable group containing a C═C double bond is at least one selected from the group consisting of an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group. The cured film forming composition as described.   (C) The cured film forming composition of Claim 1 or 2 which further contains at least 1 type chosen from the group which consists of the monomer and polymer which have a polymeric group containing a C = C double bond.   The cured film forming composition as described in any one of Claims 1 thru | or 3 which contains 0.1 mass part-50 mass parts (B) component based on 100 mass parts of (A) component.   The cured film forming composition of Claim 3 or 4 which contains 10 mass parts thru | or 1000 mass parts (C) component based on 100 mass parts of (A) component.   An alignment material obtained by curing the cured film forming composition according to any one of claims 1 to 5.   A phase difference material formed using a cured film obtained from the cured film forming composition according to claim 1.