JPWO2018155581A1 - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

[Problem] To provide an alignment material having excellent vertical alignment properties and capable of vertically aligning a polymerizable liquid crystal with high sensitivity even on a resin film, and a retardation material using such an alignment material. To provide a cured film-forming composition. A cured film containing (A) a polymer having a vertical alignment group, (B) a compound having two or more polymerizable groups containing a C ＝ C double bond, and (C) a radical polymerization initiator A cured film-forming composition, an alignment material, and a retardation material, wherein the composition substantially has only a component (B) having a polymerizable group containing a C = C double bond. [Selection diagram] 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 creating + 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, a proposal has been made to use the + C plate in order to improve the viewing angle characteristics of a circularly polarizing plate used as an antireflection film for an organic EL display (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 formation. 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.

  Therefore, there is a need for an alignment material that 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, An object of the present invention is to provide a cured film forming composition for providing an alignment material capable of stably aligning a polymerizable liquid crystal vertically under low-temperature and short-time firing conditions even on a resin film.

Another object of the present invention is obtained from the cured film-forming composition, having excellent vertical orientation, solvent resistance, and stable polymerization on a resin film under low-temperature and short-time firing conditions. Another object of the present invention is to provide a phase difference material useful for an alignment material capable of vertically aligning a crystalline liquid crystal and a + C plate formed using the alignment material.
Other objects and advantages of the present invention will become apparent from the following description.

  As a result of intensive studies to achieve the above object, the present inventors have found that a cured film based on a polymer having a vertically aligning group and a compound having two or more polymerizable groups containing a C═C double bond. It has been found that a cured film having excellent vertical alignment can be formed by selecting a forming material, and the present invention has been completed.

（式［１］中、
Ｙ¹は単結合を表すか、又は、−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である結合基を表し、
Ｙ²は単結合、直鎖状又は枝分かれ状の炭素原子数１〜１５のアルキレン基（該アルキレン基は、１ないし３個の結合基Ａで中断され得るが、但し、結合基Ａ同士が結合することはない。）若しくは−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−を表すか、又は、ベンゼン環、シクロヘキサン環または複素環から選ばれる２価の環状基（該２価の環状基は、該環状基上の任意の水素原子が、直鎖状又は枝分かれ状の炭素原子数１〜３のアルキル基、直鎖状又は枝分かれ状の炭素原子数１〜３のアルコキシル基、直鎖状又は枝分かれ状の炭素原子数１〜３のフッ素含有アルキル基、直鎖状又は枝分かれ状の炭素原子数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。）を表し、
Ｙ³は単結合または炭素原子数１〜１５のアルキレン基（該アルキレン基は、直鎖状、枝分かれ状、又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、１ないし３個の結合基Ａで中断され得るが、但し、結合基Ａ同士が結合することはない。）を表し、
Ｙ⁴は単結合を表すか、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（該２価の環状基は、該環状基上の任意の水素原子が、直鎖状又は枝分かれ状の炭素原子数１〜３のアルキル基、直鎖状又は枝分かれ状の炭素原子数１〜３のアルコキシル基、直鎖状又は枝分かれ状の炭素原子数１〜３のフッ素含有アルキル基、直鎖状又は枝分かれ状の炭素原子数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。）を表すか、又は、ステロイド骨格を有する炭素原子数１７〜３０の２価の有機基を表し、
Ｙ⁵はベンゼン環、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（該２価の環状基は、該環状基上の任意の水素原子が、直鎖状又は枝分かれ状の炭素原子数１〜３のアルキル基、直鎖状又は枝分かれ状の炭素原子数１〜３のアルコキシル基、直鎖状又は枝分かれ状の炭素原子数１〜３のフッ素含有アルキル基、直鎖状又は枝分かれ状の炭素原子数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。）を表し、
ｎは０〜４の整数を表し、ｎが２以上の場合、それぞれのＹ⁵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のアルコキシル基または炭素原子数１〜１８のフッ素含有アルコキシル基（該炭素原子数１〜１８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は、直鎖状、枝分かれ状、又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、１ないし３個の結合基Ａで中断され得るが、但し、結合基Ａ同士が結合することはない。）を表し、
Ｙ²及びＹ³が単結合以外の基を表す場合、Ｙ²とＹ³との結合は、単結合であっても、結合基Ａを介してなされていてもよく、
Ｙ³及びＹ⁴が単結合以外の基を表す場合、Ｙ³とＹ⁴との結合は、単結合であっても、結合基Ａを介してなされていてもよく、
Ｙ⁴及びＹ⁵が単結合以外の基を表す場合、Ｙ⁴とＹ⁵との結合は、単結合であっても、結合基Ａを介してなされていてもよく、
Ｙ⁵及びＹ⁶が単結合以外の基を表す場合、Ｙ⁵とＹ⁶との結合は、単結合であっても、結合基Ａを介してなされていてもよく、
ｎが２以上である場合、１つのＹ⁵と、これに隣接するＹ⁵との結合は、単結合であっても、結合基Ａを介してなされていてもよく、
結合基Ａ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、式［１］で表される基中に含まれる炭素原子の数の合計は６〜３０である。）。That is, the present invention as a first aspect,
(A) a polymer having a group represented by the following formula [1] as a vertical alignment group;
(B) a cured film-forming composition containing a compound having two or more polymerizable groups containing a C═C double bond, and (C) a radical polymerization initiator,
The present invention relates to a cured film-forming composition characterized in that substantially only component (B) has a polymerizable group containing a C═C double bond.

(In Formula [1],
Y ¹ represents a single bond or consists of —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—. Represents a linking group which is a group selected from the group;
Y ² is a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms (the alkylene group may be interrupted by 1 to 3 bonding groups A, provided that the bonding groups A are bonded to each other) . never be) or -CH ₂ -CH (OH) -CH ₂ - or represents, or a divalent cyclic group (the divalent cyclic group selected from benzene ring, cyclohexane ring or heterocyclic ring, Arbitrary hydrogen atoms on the cyclic group are linear or branched alkyl groups having 1 to 3 carbon atoms, linear or branched alkoxy groups having 1 to 3 carbon atoms, linear or branched And optionally substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a linear or branched fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms (the alkylene group may be linear, branched or cyclic, or a combination thereof, and 1 to 3 bonding groups) Which can be interrupted at A, provided that the linking groups A are not bonded together).
Y ⁴ represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring (in the divalent cyclic group, any hydrogen atom on the cyclic group is linear or branched) A straight-chain or branched alkoxy group having 1 to 3 carbon atoms, a straight-chain or branched alkyl group having 1 to 3 carbon atoms, a straight-chain Or a branched or branched fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom, or a divalent organic group having 17 to 30 carbon atoms having a steroid skeleton. Represents
Y ⁵ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring (the divalent cyclic group is an arbitrary hydrogen atom on the cyclic group having a linear or branched carbon atom number of 1 -3 alkyl groups, linear or branched alkoxy groups having 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl groups having 1 to 3 carbon atoms, linear or branched carbons Which may be substituted with a fluorine-containing alkoxyl group having 1 to 3 atoms or a fluorine atom)
n represents an integer of 0 to 4, and when n is 2 or more, each 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 ( The alkyl group having 1 to 18 carbon atoms, the fluorine-containing alkyl group having 1 to 18 carbon atoms, the alkoxyl group having 1 to 18 carbon atoms and the fluorine-containing alkoxyl group having 1 to 18 carbon atoms are linear or branched. Or any one of them or a combination thereof, which may be interrupted by 1 to 3 bonding groups A, provided that the bonding groups A are not bonded to each other).
When Y ² and Y ³ represent a group other than a single bond, the bond between Y ² and Y ³ may be a single bond or a bond group A,
If Y ³ and Y ⁴ represents a group other than a single bond, the bond between Y ³ and Y ⁴ may be a single bond, it may also be made via the linking group A,
If Y ⁴ and Y ⁵ represents a group other than a single bond, the bond between Y ⁴ and Y ⁵ may be a single bond, it may also be made via the linking group A,
If Y ⁵ and Y ⁶ represents a group other than a single bond, the bond between Y ⁵ and Y ⁶ may be a single bond, it may also be made via the linking group A,
When n is 2 or more, the bond between one Y ⁵ and the adjacent Y ⁵ may be a single bond or a bond A,
The linking group A is a group selected from the group consisting of —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—. Represent,
However, the total number of carbon atoms contained in the group represented by the formula [1] is 6-30. ).

As a second aspect, the polymerizable group containing a C═C double bond as the component (B) is at least one selected from 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.
As 3rd viewpoint, based on 100 mass parts of (A) component, it is related with the cured film formation composition as described in the 1st viewpoint or 2nd viewpoint containing 10 mass parts-2000 mass parts (B) component.
As 4th viewpoint, the cured film formation composition in any one of the 1st viewpoint thru | or 3rd viewpoint containing 0.1 mass part-50 mass parts (C) component per 100 mass parts of (A) component. Related to things.

As a fifth aspect, the present invention relates to an alignment material obtained by curing the cured film forming composition according to any one of the first to fourth aspects.
As a sixth 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 to fourth aspects.

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 third aspect of the present invention, it is possible to provide a retardation material that can be formed on a resin film with high efficiency, is highly transparent, and has high solvent resistance.

<Curing film forming composition>
The cured film forming composition of the present invention comprises (A) a polymer having a vertical alignment group as a component, (B) a compound having two or more polymerizable groups containing a C═C double bond, and ( And a radical polymerization initiator as component C), and only component (B) has a polymerizable group containing a C═C double bond. 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.

式［１］中、は単結合を表すか、又は、−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である結合基を表す。
式［１］中、Ｙ²は単結合または直鎖状又は枝分かれ状の炭素原子数１〜１５のアルキレン基を表し、該アルキレン基は、１ないし３個の結合基Ａで中断され得るが、但し、結合基Ａ同士が結合することはない。
Ｙ²として、−ＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−も挙げられる。
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、直鎖状又は枝分かれ状の炭素原子数１〜３のアルキル基、直鎖状又は枝分かれ状の炭素原子数１〜３のアルコキシル基、直鎖状又は枝分かれ状の炭素原子数１〜３のフッ素含有アルキル基、直鎖状又は枝分かれ状の炭素原子数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 the formula [1], represents a single bond, or —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—. It represents a linking group that is a group selected from the group consisting of NH-.
In the formula [1], Y ² represents a single bond or a linear or branched alkylene group having 1 to 15 carbon atoms, and the alkylene group can be interrupted by 1 to 3 bonding groups A. However, the bonding groups A are not bonded to each other.
Y ² also includes —CH ₂ —CH (OH) —CH ₂ —.
Y ^{2 includes a} divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on the cyclic group is a linear or branched carbon atom having 1 to 3 carbon atoms. Alkyl group, linear or branched alkoxyl group having 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl group having 1 to 3 carbon atoms, linear or branched carbon atom number 1 -3 fluorine-containing alkoxyl groups or fluorine atoms may be substituted.

  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 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, and the alkylene group is linear, branched, cyclic, or a combination thereof. Alternatively, it may be interrupted by 1 to 3 linking groups A, provided that the linking groups A are not bonded together.
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 linear or A branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched alkyl group having 1 to 3 carbon atoms, straight It may be substituted with a linear or branched 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 for Y ² above.

（式中、＊は結合位置を表す。）Furthermore, Y ⁴ may be a divalent organic group selected from organic groups having 17 to 30 carbon atoms 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.

(In the formula, * represents a bonding position.)

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

In the formula [1], 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 linear or branched carbon atom number. 1 to 3 alkyl groups, linear or branched alkoxyl groups having 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl groups having 1 to 3 carbon atoms, linear or branched It may be substituted with 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 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. A fluorine-containing alkoxyl group, wherein the alkyl group has 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 having 1 to 18 carbon atoms. The group may be linear, branched, cyclic, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A provided that the bonding groups A are bonded to each other. Absent.

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 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferably, Y ⁶ is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

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

  For example, the alkyl group having 1 to 18 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group. Group, 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-dimethyl-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 Ru-n-butyl group, 1-methyl-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 and the like.

As said C1-C15 alkylene group, the bivalent group which removed one arbitrary hydrogen atom from the said alkyl group can be mentioned.
As said C1-C18 alkoxyl group, the group which oxygen atom -O- couple | bonded with the group quoted as the specific example of the said alkyl group can be mentioned.
The fluorine-containing alkyl group having 1 to 18 carbon atoms and the fluorine-containing alkoxyl group having 1 to 18 carbon atoms include the alkyl group having 1 to 18 carbon atoms and the alkoxyl group having 1 to 18 carbon atoms. A group in which any hydrogen atom is substituted with a fluorine atom can be exemplified.

Furthermore, if the Y ² and Y ³ represents a group other than a single bond, the bond between Y ² and Y ³ may be a single bond, may also be made via the linking group A, Y ³ and Y ^{In the} case where ⁴ represents a group other than a single bond, the bond between Y ³ and Y ⁴ may be a single bond or may be made through a bonding group A, and Y ⁴ and Y ⁵ may be other than a single bond. In the case of representing a group, the bond between Y ⁴ and Y ⁵ may be a single bond or may be made through a bonding group A. When Y ⁵ and Y ⁶ represent a group other than a single bond, Y The bond between ⁵ and Y ⁶ may be a single bond or via a bonding group A. When n is 2 or more, one Y ⁵ and Y ⁵ adjacent thereto are The bond may be a single bond or may be made through the bonding group A.

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

  In addition, the sum total of the number of carbon atoms contained in group represented by Formula [1] is 6-30, for example, 6-20.

  Among these, considering the vertical alignment and the coating property of the polymerizable liquid crystal, the vertical alignment group represented by the formula [1] is a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms. It is preferable that it is a C7-C18, especially 8-15 alkyl group.

  The method for obtaining the polymer of component (A) of the present invention is not particularly limited. For example, the polymer of the component (A) can be obtained by reacting a monomer having a vertical alignment group and an arbitrary monomer by a polymerization method such as radical polymerization.

  Specific examples of arbitrary monomers are given below. 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, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene and 1,7. -Octadiene monoepoxide and the like.

  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.

  Examples of acrylic ester compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate. , Phenyl acrylate, glycidyl 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, - propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and the like 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate. , Phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3 -Methoxybutyl methacrylate Examples include 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate. .

  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 maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  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 solvent is too small. Resistance and heat resistance may decrease.

  In the polymer of component (A), the proportion of the vertically aligning group is preferably 3 mol% to 90 mol%, more preferably 5 mol% to 80 mol%, per 100 mol of all repeating units of the polymer. . When the amount is less than 3 mol%, the vertical alignment property may be insufficient, and when it is more than 90 mol%, the liquid crystal coating property may be adversely affected.

  Commercially available products can be suitably used as the polymer having a vertical alignment group, and examples thereof include ARUFON UF-5041, UF-5080, and UF-5022 [all are manufactured by Toagosei Co., Ltd.].

<(B) component>
The component (B) in the cured film-forming composition of the present invention is a compound having two or more polymerizable groups containing a C═C double bond.
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 as the component (B) preferably has 3 to 16 carbon atoms and has an unsaturated bond at the end, as in the formula (b2) The particular side chain represented is particularly preferred.

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有機基、または、この群から選ばれる複数の有機基の組み合わせからなる有機基である。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 an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or from this group An organic group comprising a combination of a plurality of organic groups selected. R ⁵¹ may contain an ester bond, an ether bond, an amide 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.

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-.

  As examples of the compound having a polymerizable group containing a C═C double bond, examples of suitable compounds will be given below, but the component (B) is not limited to these examples.

  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, Intererythritol di (meth) acrylate, tricyclo [5.2.1.02,6] decandimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxy Propane, 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. It is.

  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 1206PE, 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, the same A-DPH [all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; DPHA [manufactured by Daicel Ornex Co., Ltd.] Can be mentioned.

  Examples of the bifunctional urethane (meth) acrylate include a urethanized product of a phenylglycidyl ether (meth) acrylic acid adduct and hexamethylene diisocyanate, and a 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.] Oligo U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA-33H [all of which are 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 (B) of the present invention may be a polymer compound having a side chain in which one or more 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 (B) is preferably 1,000 to 200,000, more preferably 5,000 to 50,000. When the molecular weight is less than 1,000, the effect of the present invention is not achieved. On the other hand, if the molecular weight exceeds 100,000, it may not dissolve in the composition.

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

  (B) Content in the case of containing a component is 10 mass parts-2000 mass parts per 100 mass parts of (A) component, Preferably, it is 15 mass parts-500 mass parts.

<(C) component>
Component (C) 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.
As commercially available products, Irgacure 184, 369, 379EG, 651, 500, 907, CGI369, CG24-61 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucyrin LR8728, Lucyrin TPO (above, manufactured by BASF Corporation), Examples include Darocur 1116, 1173 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Ubekrill P36 (manufactured by UCB Co., Ltd.), and other commercial names.

  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, A combination of 4′-diethylaminobenzophenone and mercaptobenzothiazole, Lucillin TPO (trade name), Irgacure 651 (trade name), and Irgacure 369 (trade name) are 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.

<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 should just dissolve (A) component, (B) component, (C) component, and the other additive mentioned later as needed, and the kind and structure are not specifically limited.

  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 comprises (A) a polymer having a vertically-alignable group, (B) a compound having two or more polymerizable groups containing a C═C double bond, and (C) component. The polymerization initiator may further contain other additives as long as the effects of the present invention are not impaired. 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]: Based on 100 parts by mass of the component (A) and the component (A), 0.1 part by mass to 100 parts by mass of the polymer as the component (B) and the component (A) of 10 parts by mass to 2000 parts by mass. The cured film formation composition containing the (C) component of 50 mass parts of mass parts.
[2]: Based on 100 parts by mass of component (A) and component (A), 0.1 part by mass to 100 parts by mass of the polymer as component (B) and component (A) of 10 to 2000 parts by mass. The cured film forming composition containing (C) component of a mass part-50 mass parts, 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.

ＡＩＢＮ：α， α’ − アゾビスイソブチロニトリル
ＡＲＵ：東亞合成（株）製 ＡＲＵＦＯＮ ＵＦ−５０４１
＜（Ｂ）成分＞
ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート
８ＫＸ：大成ファインケミカル（株）製 ８ＫＸ−０７８ （固形分濃度４０質量％）
８ＫＱ：大成ファインケミカル（株）製 ８ＫＱ−２００１ （固形分濃度３９質量％）
８ＵＨ：大成ファインケミカル（株）製 ８ＵＨ−１００６ （固形分濃度４５質量％）
＜（Ｃ）成分＞
ＩＲＧ：ＢＡＳＦ社製 ＩＲＧＡＣＵＲＥ ９０７
＜溶媒＞
実施例及び比較例の各樹脂組成物は溶剤を含有し、その溶剤として、プロピレングリコールモノメチルエーテル（ＰＭ）、酢酸エチル（ＥＡ）、酢酸ブチル（ＢＡ）を用いた。
＜重合体の分子量の測定＞
重合例におけるアクリル共重合体の分子量は、（株）島津製作所製ＧＰＣ装置（Ｓｈｏｄｅｘ（登録商標）カラムＫＦ８０３ＬおよびＫＦ８０４Ｌ）を用い以下のようにして測定した。なお、下記の数平均分子量（以下、Ｍｎと称す）および数平均分子量（以下、Ｍｗと称す）はポリスチレン換算値にて表した。
溶離液：テトラヒドロフラン
流量：１ｍＬ／ｍｉｎ
カラム温度：４０°Ｃ
検量線作成用標準サンプル：昭和電工製 ポリスチレン（分子量 約 １９７，０００、５５，１００、１２，８００、３，９５０、１，２６０、５８０）Hereinafter, although an example is given and the present invention is explained in more detail, the present invention is not limited to these examples.
[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Raw material of component (A)>
LAA: lauryl acrylate MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate MA1:

AIBN: α, α′-azobisisobutyronitrile ARU: ARUFON UF-5041 manufactured by Toagosei Co., Ltd.
<(B) component>
DPHA: dipentaerythritol hexaacrylate 8KX: manufactured by Taisei Fine Chemical Co., Ltd. 8KX-078 (solid content concentration 40% by mass)
8KQ: Taisei Fine Chemical Co., Ltd. 8KQ-2001 (solid content concentration 39% by mass)
8UH: Taisei Fine Chemical Co., Ltd. 8UH-1006 (solid content concentration 45% by mass)
<(C) component>
IRG: IRSFACURE 907 manufactured by BASF
<Solvent>
Each resin composition of the examples and comparative examples contained a solvent, and propylene glycol monomethyl ether (PM), ethyl acetate (EA), and butyl acetate (BA) were used as the solvent.
<Measurement of molecular weight of polymer>
The molecular weight of the acrylic copolymer in the polymerization example was measured as follows using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by Shimadzu Corporation. The following number average molecular weight (hereinafter referred to as Mn) and number average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.
Eluent: Tetrahydrofuran flow rate: 1 mL / min
Column temperature: 40 ° C
Standard sample for preparing calibration curve: Polystyrene (Molecular weight: about 197,000, 55,100, 12,800, 3,950, 1,260, 580) manufactured by Showa Denko

<Synthesis Example 1> Synthesis of MA1 4- (trans-4-pentylcyclohexyl) benzoic acid 4.0 g (14.6 mmol), HEMA 1.0 g (13.3 mmol), 1- (3-dimethylaminopropyl) -3 -Ethylcarbodiimide 2.5g (15.9mmol), 4-dimethylamino pyridine 0.1g, (0.7mmol), 19.3g of tetrahydrofuran were mixed, and it stirred at room temperature for 24 hours. After completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and the residue was dissolved in 150 mL of ethyl acetate, and 100 mL of an aqueous ammonium chloride solution was added thereto and washed three times. Ethyl acetate was distilled off under reduced pressure to obtain 4.3 g of the objective product, MA1 (yield: 84%).
<Polymerization Example 1>
An acrylic copolymer solution (solid content concentration: 20% by mass) is prepared by dissolving LAA 1.0 g, MAA 3.2 g, and AIBN 0.3 g as a polymerization catalyst in PM 15.3 g and reacting at 80 ° C. for 20 hours. P1) was obtained. Mn of the obtained acrylic copolymer was 5,500 and Mw was 7,100.

<Polymerization example 2>
LAA 1.0 g, MAA 0.8 g, and AIBN 0.1 g as a polymerization catalyst were dissolved in 7.8 g of PM, and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25% by mass) ( P2) was obtained. Mn of the obtained acrylic copolymer was 13,700 and Mw was 24,000.

<Polymerization Example 3>
LAA 1.0 g, MMA 3.7 g, and AIBN 0.3 g as a polymerization catalyst were dissolved in PM 15.3 g and reacted at 80 ° C. for 20 hours, whereby an acrylic copolymer solution (solid content concentration: 25 mass%) ( P3) was obtained. Mn of the obtained acrylic copolymer was 7,700 and Mw was 13,600.

<Polymerization example 4>
MMA 3.0 g, HEMA 0.3 g, and AIBN 0.3 g as a polymerization catalyst are dissolved in 14.6 g of PM and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 30% by mass) ( P4) was obtained. Mn of the obtained acrylic copolymer was 18,000 and Mw was 32,800.
<Polymerization example 5>
Acrylic copolymer solution (solid content concentration: 20% by mass) is prepared by dissolving 1.0 g of MA1, 0.8 g of MAA, and 0.1 g of AIBN as a polymerization catalyst in 7.7 g of PM and reacting at 80 ° C. for 20 hours. P5) was obtained. Mn of the obtained acrylic copolymer was 8,900 and Mw was 30,800.

<Examples 1-11, Comparative Examples 1-2>
Each cured film forming composition was prepared with the composition shown in Table 1.

<Examples 12 to 28, Comparative Examples 3 to 5>
Next, a cured film was formed using each retardation material form composition, and vertical alignment was evaluated about each obtained cured film.
[Evaluation of vertical alignment]
Each cured film forming composition obtained in Examples 1 to 11 and Comparative Examples 1 and 2 was applied on each substrate with a wet film thickness of 4 μm using a bar coater. Each was heated and dried in a heat-circulating oven at a temperature of 110 ° C. for 60 seconds, and then this coating film was exposed to form a cured film on each substrate.
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. Each of them was heated and dried on a hot plate at a temperature of 60 ° C. for 60 seconds, and then 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 2 later.

  As shown in Table 2, the alignment materials obtained using the cured film forming compositions of the examples showed good vertical alignment properties. On the other hand, it was difficult for the cured film obtained using the cured film forming composition of the comparative example to obtain vertical alignment.

  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 (6)

(A) a polymer having a group represented by the following formula [1] as a vertical alignment group;
(B) a cured film-forming composition containing a compound having two or more polymerizable groups containing a C═C double bond, and (C) a radical polymerization initiator,
A cured film forming composition characterized in that substantially only component (B) has a polymerizable group containing a C = C double bond.

(In Formula [1],
Y ¹ represents a single bond or consists of —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—. Represents a linking group which is a group selected from the group;
Y ² is a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms (the alkylene group may be interrupted by 1 to 3 bonding groups A, provided that the bonding groups A are bonded to each other) . never be) or -CH ₂ -CH (OH) -CH ₂ - or represents, or a divalent cyclic group (the divalent cyclic group selected from benzene ring, cyclohexane ring or heterocyclic ring, Arbitrary hydrogen atoms on the cyclic group are linear or branched alkyl groups having 1 to 3 carbon atoms, linear or branched alkoxy groups having 1 to 3 carbon atoms, linear or branched And optionally substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a linear or branched fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms (the alkylene group may be linear, branched or cyclic, or a combination thereof, and 1 to 3 bonding groups) Which can be interrupted at A, provided that the linking groups A are not bonded together).
Y ⁴ represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring (in the divalent cyclic group, any hydrogen atom on the cyclic group is linear or branched) A straight-chain or branched alkoxy group having 1 to 3 carbon atoms, a straight-chain or branched alkyl group having 1 to 3 carbon atoms, a straight-chain Or a branched or branched fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom, or a divalent organic group having 17 to 30 carbon atoms having a steroid skeleton. Represents
Y ⁵ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring (the divalent cyclic group is an arbitrary hydrogen atom on the cyclic group having a linear or branched carbon atom number of 1 -3 alkyl groups, linear or branched alkoxy groups having 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl groups having 1 to 3 carbon atoms, linear or branched carbons Which may be substituted with a fluorine-containing alkoxyl group having 1 to 3 atoms or a fluorine atom)
n represents an integer of 0 to 4, and when n is 2 or more, each 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 ( The alkyl group having 1 to 18 carbon atoms, the fluorine-containing alkyl group having 1 to 18 carbon atoms, the alkoxyl group having 1 to 18 carbon atoms and the fluorine-containing alkoxyl group having 1 to 18 carbon atoms are linear or branched. Or any one of them or a combination thereof, which may be interrupted by 1 to 3 bonding groups A, provided that the bonding groups A are not bonded to each other).
When Y ² and Y ³ represent a group other than a single bond, the bond between Y ² and Y ³ may be a single bond or a bond group A,
If Y ³ and Y ⁴ represents a group other than a single bond, the bond between Y ³ and Y ⁴ may be a single bond, it may also be made via the linking group A,
If Y ⁴ and Y ⁵ represents a group other than a single bond, the bond between Y ⁴ and Y ⁵ may be a single bond, it may also be made via the linking group A,
If Y ⁵ and Y ⁶ represents a group other than a single bond, the bond between Y ⁵ and Y ⁶ may be a single bond, it may also be made via the linking group A,
When n is 2 or more, the bond between one Y ⁵ and the adjacent Y ⁵ may be a single bond or a bond A,
The linking group A is a group selected from the group consisting of —O—, —CH ₂ O—, —COO—, —OCO—, —NHCO—, —NH—CO—O— and —NH—CO—NH—. Represent,
However, the total number of carbon atoms contained in the group represented by the formula [1] is 6-30. ).   (B) The cured film forming composition of Claim 1 whose polymeric group containing the C = C double bond of a component is at least 1 type chosen from an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group. Stuff.   (A) The cured film formation composition of Claim 1 or 2 containing 10 mass parts-2000 mass parts (B) component based on 100 mass parts component.   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 (C) component per 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 4.   A retardation material formed using a cured film obtained from the cured film-forming composition according to claim 1.