JP7249271B2 - Cured film-forming composition, alignment material and retardation material - Google Patents

Description

TECHNICAL FIELD 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). ; LCD) and the viewing angle characteristics of the circular polarizer used as an antireflection film for organic EL displays. It 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 liquid crystal molecules do not tilt in the vertical direction. be done. For example, as disclosed in Patent Document 1, the IPS-LCD at the initial stage of proposal does not use a viewing angle compensation film, and an IPS-LCD that does not use such a viewing angle compensation film has a tilt angle. It has the disadvantage of exhibiting low contrast ratio values due to the relatively large light leakage in the dark state.

Patent Document 2 discloses an IPS-LCD compensation film using a +C plate and a +A plate (positive A plate). This document describes the following configuration of the liquid crystal display device described therein.
1) A horizontally aligned liquid crystal layer is sandwiched between two substrates supplied by electrodes capable of applying an electric field parallel to the liquid crystal layer surface.
2) At least one +A plate and +C plate are sandwiched between both polarizers.
3) The principal optic axis of the +A plate is perpendicular to the principal optic axis of the liquid crystal layer.
4) The retardation value R _LC of the liquid crystal layer, the retardation value R _+C of the +C plate, and the retardation value R _+A of the +A plate are determined so as to satisfy the following equations.
R _LC : R _+C : R _+A ≈1:0.5:0.25
5) The relationship between the retardation values of the +A plate and the +C plate and the retardation value in the thickness direction of the protective film of the polarizing plate is not shown (TAC, COP, PNB).

Also, the +A plate aimed at providing an IPS-LCD with high contrast characteristics in front and tilt angles, low color shift by minimizing dark state light leakage at tilt angles. and a +C plate are disclosed (Patent Document 3). Furthermore, a proposal has been made to use a +C plate 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-2-256023 JP-A-11-133408 JP 2009-122715 A Japanese Patent Application Laid-Open No. 2001-281669 JP 2015-79256 A

As previously proposed, the +C plate can compensate for light leakage when the viewing angle of the polarizer is large. It is very useful as an optical compensation film. However, it is difficult to develop the vertical orientation (positive C plate) property by the conventionally known stretching treatment method.

In addition, conventionally proposed vertical alignment films using polyimide require the use of a polyimide solvent such as N-methyl-2-pyrrolidone in film formation. For this reason, there is no problem with a glass substrate, but when the substrate is a film, there is a problem that the substrate is damaged during the formation of the alignment film. In addition, a vertical alignment film using polyimide requires baking at a high temperature, and there is a problem that the film substrate cannot withstand high temperatures.
Furthermore, a method of forming a vertical alignment film by directly treating a substrate with a silane coupling agent or the like having a long-chain alkyl has been proposed. There is a problem that the treatment is difficult and the base material is limited (Patent Document 4).

In recent years, in response to the demand for production cost reduction, so-called roll-to-roll production on inexpensive resin films such as TAC (triacetyl cellulose) films and COP (cycloolefin polymer) films has been demanded. However, it has been difficult to manufacture a +C plate on a resin film with an alignment film formed from the conventional materials as described above.

Therefore, there is a demand for an alignment material capable of forming 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 based on the above findings and examination results, and the problem to be solved is to have excellent vertical alignment, 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 vertically aligning polymerizable liquid crystals stably even on a resin film under low-temperature and short-time baking conditions.

Another object of the present invention is to obtain from the cured film-forming composition, have excellent vertical orientation, have solvent resistance, and stably polymerize even on a resin film under low-temperature and short-time baking conditions. To provide an alignment material capable of vertically aligning liquid crystals and a retardation material useful for a +C plate formed by using the alignment material.
Other objects and advantages of the invention will become apparent from the following description.

In order to achieve the above object, the present inventors have made intensive studies and found that a cured film based on a polymer having a vertically aligned group and a compound having two or more polymerizable groups containing a C═C double bond The inventors have found that a cured film having excellent vertical alignment can be formed by selecting the forming material, and completed the present invention.

（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, as a first aspect of the present invention,
(A) a polymer having a group represented by the following formula [1] as a vertically aligned group,
(B) a compound having two or more polymerizable groups containing a C═C double bond, and (C) a cured film-forming composition containing a radical polymerization initiator,
The cured film-forming composition is characterized in that substantially only the 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 bonding group that 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 linking groups A, provided that the linking groups A or —CH ₂ —CH(OH)—CH ₂ —, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring (the divalent cyclic group is Any hydrogen atom on the cyclic group is a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxyl group having 1 to 3 carbon atoms, or a linear or branched chain. 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 optionally substituted with a fluorine atom),
Y ³ is 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 has 1 to 3 can be interrupted by A, provided that the bonding groups A do not bond to each other.),
Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring (the divalent cyclic group is a linear or branched linear or branched alkyl group having 1 to 3 carbon atoms, 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 optionally substituted with a 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 such that any hydrogen atom on the cyclic group is linear or branched and has 1 carbon atom -3 alkyl groups, linear or branched alkoxyl groups of 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl groups of 1 to 3 carbon atoms, linear or branched carbon 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 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 a fluorine-containing alkoxyl group having 1 to 18 carbon atoms (such Alkyl groups having 1 to 18 carbon atoms, fluorine-containing alkyl groups having 1 to 18 carbon atoms, alkoxyl groups having 1 to 18 carbon atoms and fluorine-containing alkoxyl groups having 1 to 18 carbon atoms are linear or branched. , or may be cyclic or a combination thereof, and may be interrupted by 1 to 3 linking groups A, provided that linking groups A are not linked 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 via a bonding group A,
When Y ³ and Y ⁴ represent a group other than a single bond, the bond between Y ³ and Y ⁴ may be a single bond or via a bonding group A,
When Y ⁴ and Y ⁵ represent a group other than a single bond, the bond between Y ⁴ and Y ⁵ may be a single bond or via a bonding group A,
When Y ⁵ and Y ⁶ represent a group other than a single bond, the bond between Y ⁵ and Y ⁶ may be a single bond or via a bonding group A,
When n is 2 or more, the bond between one Y ⁵ and its adjacent Y ⁵ may be a single bond or via a bonding group 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 formula [1] is 6-30. ).

As a second aspect, described in the first aspect, wherein the polymerizable group containing a C=C double bond of the component (B) is at least one selected from an acrylic group, a methacrylic group, a vinyl group, an allyl group and a maleimide group. It relates to a cured film-forming composition of.
As a third aspect, it relates to the cured film-forming composition according to the first or second aspect, which contains 10 parts by mass to 2000 parts by mass of component (B) based on 100 parts by mass of component (A).
As a fourth aspect, the cured film-forming composition according to any one of the first to third aspects, containing 0.1 parts by mass to 50 parts by mass of component (C) per 100 parts by mass of component (A). about things.

As a fifth aspect, it relates to an alignment material characterized by being obtained by curing the cured film-forming composition according to any one of the first to fourth aspects.
As a sixth aspect, it 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 a first aspect of the present invention, to provide an alignment material that has excellent vertical alignment properties and can stably vertically align a polymerizable liquid crystal even on a resin film under low-temperature, short-time baking conditions. A useful cured film-forming composition 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 properties and can stably vertically align polymerizable liquid crystals under low-temperature, short-time baking conditions.
According to the third aspect of the present invention, it is possible to provide a retardation material that can be formed even on a resin film with high efficiency and has high transparency and high solvent resistance.

<Cured film forming composition>
The cured film-forming composition of the present invention comprises a polymer having a vertically aligned group as component (A), a compound having two or more polymerizable groups containing a C=C double bond as component (B), and ( and a radical polymerization initiator as component C), and substantially only component (B) has a polymerizable group containing a C═C double bond. Other additives may be added as long as they do not impair the effects of the present invention.
The details of each component are described below.

<(A) Component>
Component (A) contained in the cured film-forming composition of the present invention is a polymer having a vertically oriented 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 formula [1], represents a single bond, or -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO- represents a bonding group selected from the group consisting of NH—;
In 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 may be interrupted by 1 to 3 bonding groups A, However, the bonding groups A do not bond to each other.
Y ² also includes -CH ₂ -CH(OH)-CH ₂ -.
Further, Y ² includes a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is a linear or branched C 1-3 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 1 carbon atom It may be substituted with ∼3 fluorine-containing alkoxyl groups or fluorine atoms.

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, more preferred. 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 and benzimidazole ring.

Examples of the alkyl group mentioned as the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and a cyclopropyl group, and examples of the alkoxyl group include oxygen A group to which the atom -O- is attached can be mentioned. Examples of the fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group or 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, or cyclic, or a combination thereof. may be interrupted by 1 to 3 linking groups A, provided that linking groups A are not linked to each other.
In the above formula [1], ^Y represents a single bond or 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 linear or A branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxyl group having 1 to 3 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 3 carbon atoms, a linear It may be substituted with a chain or branched fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom.

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

（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 and having a steroid skeleton. Preferred examples thereof are cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erigosteryl, estril, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, melatranil, methyltestosteryl, norethisteryl, pregnenonyl, β-sitosteryl, It is a divalent group having a structure in which two hydrogen atoms are removed from a structure selected from stigmasteryl, testosteryl, cholesteryl acetate and the like. More specifically, for example, it is as follows.

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

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

In formula [1], Y 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 has 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 heterocyclic ring and the alkyl group and the like mentioned as 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 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. Of these, n is preferably 0 to 3 from the viewpoint of raw material availability and ease of synthesis. 0-2 is more preferred.

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 of 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 group may be linear, branched, or cyclic, or combinations thereof, and may be interrupted by 1 to 3 linking groups A, provided that linking groups A are not linked to each other. do not have.

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. More preferably, Y ⁶ is an alkyl group of 1-12 carbon atoms or an alkoxyl group of 1-12 carbon atoms. Particularly preferably, Y ⁶ is an alkyl group of 1-9 carbon atoms or an alkoxyl group of 1-9 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, 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-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.

Examples of the alkylene group having 1 to 15 carbon atoms include a divalent group obtained by removing one arbitrary hydrogen atom from the above alkyl group.
Examples of the alkoxyl group having 1 to 18 carbon atoms include groups in which an oxygen atom -O- is bonded to the groups given as specific examples of the alkyl group.
In addition, as the fluorine-containing alkyl group having 1 to 18 carbon atoms and the fluorine-containing alkoxyl group having 1 to 18 carbon atoms, A group in which any hydrogen atom is substituted with a fluorine atom can be mentioned.

Furthermore, 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 via a bonding group A, and Y ³ and Y When 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 via a bonding group A, and Y ⁴ and Y ⁵ may be a single bond other than a single bond. When representing a group, the bond between Y ⁴ and Y ⁵ may be a single bond or via 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, and when n is 2 or more, one Y ⁵ and its adjacent Y ⁵ The bond may be a single bond or via a linking group A.

The bonding group A is -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-;

The total number of carbon atoms contained in the group represented by formula [1] is 6-30, for example 6-20.

Among these, considering the vertical alignment property and the applicability 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. and more preferably an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms.

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

Specific examples of optional monomers are given below. However, it is not limited to these.

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

Monomers having an epoxy group include, for example, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene and 1,7 - Octadiene monoepoxide and the like.

Examples of monomers 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-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and the like.

Monomers having amino groups include, for example, 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

Monomers having a phenolic hydroxy group include, for example, hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide and N-(hydroxyphenyl)maleimide.

Monomers having isocyanate groups include, for example, acryloylethyl isocyanate, methacryloylethyl isocyanate and m-tetramethylxylene isocyanate.

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, and 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, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate. .

Examples of methacrylic ester compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, and anthrylmethyl 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, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl A methacrylate etc. are mentioned.

Examples of vinyl compounds include methyl vinyl ether, benzyl vinyl ether, vinylnaphthalene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

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

Maleimide compounds include, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and 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 exceeds 200,000, the solubility in the solvent may decrease and the handling property may deteriorate. Tolerance and heat resistance may decrease.

In the polymer of component (A), the proportion of the vertically aligned group present is preferably 3 mol % to 90 mol %, more preferably 5 mol % to 80 mol %, per 100 mol of all repeating units of the polymer. . If it is less than 3 mol %, the vertical alignment may be insufficient, and if it is more than 90 mol %, the applicability of the liquid crystal may be adversely affected.

As the polymer having a vertically oriented group, commercially available products can be suitably used, and examples thereof include ARUFON UF-5041, UF-5080, and UF-5022 [all 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 C═C double bonds.
Polymerizable groups containing C=C double bonds include acrylic groups, methacrylic groups, vinyl groups, allyl groups, maleimide groups, and the like.

The polymerizable group containing a C=C double bond of component (B) preferably has 3 to 16 carbon atoms and has an unsaturated bond at the end, and is represented by formula (b2) The particular side chains depicted are 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 It is an organic group consisting of a combination of a plurality of selected organic groups. R ⁵¹ may contain an ester bond, an ether bond, an amide bond, a urethane bond, or the like.
In formula (b2), R ⁵² is a hydrogen atom or a methyl group, a specific side chain in which R ⁵² is a hydrogen atom is preferred, and a specific side chain in which the terminal is an acryloyl group, a methacryloyl group or a styryl group is more preferred. be.

In addition, in this specification, a (meth)acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid refers to acrylic acid and methacrylic acid. The (meth)acryloyl group represents CH ₂ =CHCO- and CH(CH ₃ )=CHCO-.

Preferred examples of compounds having a polymerizable group containing a C═C double bond are listed below, but component (B) is not limited to these examples.

Examples of compounds 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, 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 acrylates, tricyclo[5.2.1.02,6]decandimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 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-adamantanedimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate and the like.

Commercially available compounds having two or more (meth)acryloyl groups can be suitably used, 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 Ester 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 [all manufactured by Kyoeisha Chemical Co., Ltd.]; 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, 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, HD-N, NOD-N, NPG, 1206PE , 701, 9PG [all manufactured by Shin-Nakamura Chemical Co., Ltd.]; FANCRYL FA-124AS, FA-129AS, 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 manufactured by Hitachi Chemical Co., Ltd.]; Trademark) 11, HPDNA [manufactured by Daicel Allnex Co., Ltd.]; Viscoat #195, #230, #260, #310HP, #335HP, #700HV, #540, #802, #295 [These are all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like.

Compounds having three (meth)acryloyl groups (trifunctional compounds) 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 moles 3-30], propylene oxide-modified trimethylolpropane tri(meth)acrylate [propylene oxide addition moles 3-30], ethylene oxide-modified glycerin tri(meth)acrylate [ethylene oxide addition moles 3 to 30], propylene oxide-modified glycerin tri(meth)acrylate [propylene oxide addition mole number 3 to 30], tris(2-(acryloyloxy)ethyl)isocyanurate, ε-caprolactone-modified tris(2-(acryloyloxy ) ethyl) isocyanurate [ε-caprolactone addition mole number 1 to 30], 1,1,1-trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin tri(meth)acrylate and the like.

Commercially available products can be suitably used as the trifunctional compound, such as Viscoat #360 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; NK ester A-GLY-9E, A-GLY-20E, AT-20E [above , all manufactured by Shin-Nakamura Chemical Co., Ltd.]; Organic Chemical Industry Co., Ltd.]; Light Acrylate TMP-A, Light Ester PE-3A, Light Ester TMP [All of these are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9300, A-9300-1CL, the same A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT [all manufactured by Shin-Nakamura Chemical Co., Ltd.]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [both of which are manufactured by Daicel Allnex Co., 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 [ 4 to 40 moles of ethylene oxide], ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like.

Commercially available products can be suitably used as the above tetrafunctional compounds, such as NK Ester ATM-4E and ATM-35E [both of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; Co., Ltd.], etc., Viscoat #300 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light Acrylate PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester AD-TMP, A-TMMT [all of the above] manufactured by Shin-Nakamura Chemical Co., Ltd.];

Compounds having 5 or more (meth)acryloyl groups (pentafunctional or higher compounds) include, for example, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate [ethylene oxide addition mole number 6 to 60], ethylene oxide-modified tripentaerythritol octa ( meth)acrylate [ethylene oxide addition mole number 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 penta- or higher-functional compounds. Acrylate DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9550, A-DPH [both of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; DPHA [manufactured by Daicel Allnex Co., Ltd.] mentioned.

Bifunctional urethane (meth)acrylates include, for example, a urethanized product of a (meth)acrylic acid adduct of phenyl glycidyl ether and hexamethylene diisocyanate, and a urethanized product of a (meth)acrylic acid adduct of phenyl glycidyl ether and toluene diisocyanate. etc.

The bifunctional urethane (meth)acrylate can be suitably used as a commercial product, for example, AH-600, AT-600 [both 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 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 [all of which are manufactured by Daicel Allnex Co., Ltd.]; , 3300B, 3310B, 3500BA, 3520TL, 3700B, and 6640B [all of which are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.].

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.]; 205, 264, 265, 294/25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, 8667 ) product];

Specific examples of commercially available polyfunctional urethane (meth)acrylate compounds having four (meth)acryloyl groups include EBECRYL (registered trademark) 8210, 8405, and KRM (registered trademark) 8528 [all of which are Daicel Allnex Co., Ltd.]; Shiko (registered trademark) UV-7650B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd.];

Polyfunctional urethane (meth)acrylate compounds having 5 or more (meth)acryloyl groups (penta or more functional urethane (meth)acrylates) include, for example, urethane compounds of pentaerythritol tri(meth)acrylate and hexamethylene diisocyanate, urethanized products of pentaerythritol tri(meth)acrylate and toluene diisocyanate, urethanized products of pentaerythritol tri(meth)acrylate and isophorone diisocyanate, urethanized products of dipentaerythritol penta(meth)acrylate and hexamethylene diisocyanate, and the like. .

Penta- or higher-functional urethane (meth)acrylates can be suitably used as commercially available products, such as UA-306H, UA-306T, UA-306I, and UA-510H [all of which are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-6LPA, Oligo U-10HA, Oligo U-10PA, U-1100H, U-15HA, UA-53H, UA-33H [all manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 220, 1290, 5129, 8254, 8301R, KRM (registered trademark) 8200, 8200AE, 8904, 8452 [all manufactured by Daicel Allnex Co., Ltd.]; Trademark) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B [all manufactured by 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 ends are polymerizable unsaturated bonds. Polymer compounds having a side chain with a polymerizable unsaturated bond at the end preferably include polymer compounds having (meth)acryloyl groups in two or more side chains in the molecule.

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

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

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

When component (B) is included, the content is 10 to 2,000 parts by mass, preferably 15 to 500 parts by mass, per 100 parts by mass of component (A).

<(C) Component>
The (C) component 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. Thioxanthones and the like can be mentioned.

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; 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-morpholino-1-propanone, α,α Acetophenones such as -dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris(trichloromethyl)-s-triazine; [1,2′-bisimidazole]-3,3′,4,4′-tetraphenyl, [ 1,2′-bisimidazole]-1,2′-dichlorophenyl-3,3′,4,4′-tetraphenyl and other bisimidazoles, di-tert-butyl peroxide and other peroxides; 2,4 , 6-trimethylbenzoyldiphenylphosphine oxide and other acylphosphine oxides.
Commercially available products include Irgacure 184, 369, 379EG, 651, 500, 907, CGI369, CG24-61 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin LR8728, Lucirin TPO (manufactured by BASF Corporation), Commercially available products such as Darocure 1116 and 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and Uvecryl P36 (manufactured by UCB Corp.) can be mentioned.

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, tribromomethylphenylsulfone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2′-bisimidazoles and 4, Combined use of 4'-diethylaminobenzophenone and mercaptobenzothiazole, Lucilin TPO (trade name), Irgacure 651 (trade name), and Irgacure 369 (trade name) are preferred.

The above 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 based on 100 parts by mass of component (A). can be done. If the amount of the radical polymerization initiator used is less than the above range, it is likely to be affected by deactivation of radicals by oxygen (decrease in sensitivity). tend to do.

<Solvent>
The cured film-forming composition of the present invention is mainly used in the form of a solution dissolved in a solvent. The solvent used at that time is not particularly limited as long as it can dissolve the components (A), (B) and (C), and if necessary other additives described below.

Specific examples of solvents include 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 ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy -ethyl 2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone etc.

When producing an alignment material by forming a cured film on a resin film using the cured film-forming composition of the present invention, 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 exhibits resistance to the 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 may optionally contain a sensitizer, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, 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 aligned group, (B) a compound having two or more polymerizable groups containing a C═C double bond, and (C) a component. and may contain other additives as long as they do not impair the effects of the present invention. And 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]: Component (A), 10 parts by mass to 2000 parts by mass of component (B) based on 100 parts by mass of component (A), and 0.1 part per 100 parts by mass of the polymer that is component (A) A cured film-forming composition containing component (C) in an amount of 50 parts by mass to 50 parts by mass.
[2]: Component (A), 10 parts by mass to 2000 parts by mass of component (B) based on 100 parts by mass of component (A), and 0.1 part per 100 parts by mass of the polymer that is component (A) A cured film-forming composition containing component (C) in an amount of 50 parts by mass to 50 parts by mass and a solvent.

The mixing ratio, preparation method, and the like when the cured film-forming composition of the present invention is used as a solution are described in detail below.
The proportion of solids 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 % to 50% by mass, more preferably 2% to 20% by mass. Here, the solid content refers to the total components of the cured film-forming composition excluding the solvent.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, a solution of component (A) dissolved in a solvent is mixed with component (B) and further component (C) in a predetermined ratio to form a uniform solution, or this preparation method. In an appropriate stage of , if necessary, other additives are further added and mixed.

Moreover, it is preferable to use the prepared solution of the cured film-forming composition after filtering using a filter having a pore size of about 0.2 μm.

<Cured film, alignment material and retardation material>
A solution of the cured film-forming composition of the present invention is applied to a substrate (e.g., silicon/silicon dioxide coated substrate, silicon nitride substrate, metal, e.g., aluminum, molybdenum, chromium, etc. coated substrate, glass substrate, quartz substrate, ITO). substrates, etc.) and film substrates (e.g., triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene A resin film such as a film) is applied by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating following slit, inkjet coating, printing, etc. to form a coating film, and then A cured film can be formed by heating and drying with a hot plate, an oven, or the like. The cured film can be used as an alignment material as it is.

As for the conditions for heat drying, it is sufficient that the crosslinking reaction by the crosslinking agent proceeds to such an extent that the components of the cured film (orientation material) are not eluted in 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 minute to 60 minutes are employed. The heating temperature and heating time are preferably 70° C. to 160° C. and 0.5 minutes to 10 minutes.

The film thickness of the cured film (orientation material) formed using the curable composition of the present invention is, for example, 0.05 μm to 5 μm. can be selected.

The alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance. , can be oriented on an orientation material. By curing the oriented retardation material as it is, the retardation material can be formed as a layer having optical anisotropy. And when the substrate on which the alignment material is formed is a film, it is useful as a retardation film.

Further, two substrates having the alignment material of the present invention formed as described above are used, and after laminating such that the alignment materials on both substrates face each other with spacers interposed therebetween, a film is formed between the substrates. By injecting liquid crystal, a liquid crystal display element in which the liquid crystal is oriented can be obtained.
Thus, the cured film-forming composition of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display devices, and the like.

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）EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[Abbreviations used in Examples]
Abbreviations used in the following examples have the following meanings.
<Raw materials for 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: Taisei Fine Chemicals 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: IRGACURE 907 manufactured by BASF
<Solvent>
Each resin composition of 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 weights of the acrylic copolymers in the polymerization examples were measured as follows using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by Shimadzu Corporation. The number average molecular weight (hereinafter referred to as Mn) and the number average molecular weight (hereinafter referred to as Mw) below are expressed in terms of polystyrene.
Eluent: Tetrahydrofuran Flow rate: 1 mL/min
Column temperature: 40°C
Standard sample for creating a calibration curve: Showa Denko polystyrene (molecular weight about 197,000, 55,100, 12,800, 3,950, 1,260, 580)

<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 2.5 g (15.9 mmol), 4-dimethylaminopyridine 0.1 g (0.7 mmol) and tetrahydrofuran 19.3 g were mixed and stirred at room temperature for 24 hours. After completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, the residue was dissolved in 150 mL of ethyl acetate, and 100 mL of an aqueous ammonium chloride solution was added to wash three times. Ethyl acetate was distilled off under reduced pressure to obtain 4.3 g of the desired product, MA1 (yield: 84%).
<Polymerization Example 1>
1.0 g of LAA, 3.2 g of MAA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 15.3 g of PM and reacted at 80° C. for 20 hours to give an acrylic copolymer solution (solid concentration: 20% by mass) ( P1) was obtained. The obtained acrylic copolymer had an Mn of 5,500 and an Mw of 7,100.

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

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

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

<Examples 1 to 11, Comparative Examples 1 to 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 forming composition, and the vertical alignment property was evaluated for each of the obtained cured films.
[Evaluation of Vertical Alignment]
Each cured film-forming composition obtained in Examples 1 to 11 and Comparative Examples 1 and 2 was applied onto each substrate using a bar coater to give a wet film thickness of 4 μm. Each coating was dried by heating in a thermal circulation oven at a temperature of 110° C. for 60 seconds, and then exposed to light to form a cured film on each substrate.
A vertical alignment polymerizable liquid crystal solution RMS03-015 manufactured by Merck Co., Ltd. was applied to the cured film with a wet film thickness of 6 μm using a bar coater. Each film was dried by heating on a hot plate at a temperature of 60° C. for 60 seconds, and then exposed at 500 mJ/cm ² to produce a retardation material.
Incidence angle dependency of in-plane retardation of these produced retardation materials was measured using a retardation measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. Those having an in-plane retardation value of 0 at an incident angle of 0 degree and an in-plane retardation value of 38±5 nm at an incident angle of ±50 degrees were judged to be vertically aligned. The evaluation results are collectively shown in Table 2 later.

As shown in Table 2, the alignment materials obtained using the cured film-forming compositions of Examples exhibited 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 an alignment material for forming a liquid crystal alignment film of a liquid crystal display element or an optically anisotropic film provided inside or outside a liquid crystal display element. In particular, it is suitable as a material for optical compensation films for circularly polarizing plates used as antireflection films for IPS-LCDs and organic EL displays.

Claims (5)

(A) a polymer having a group represented by the following formula [1] as a vertically aligned group,
(B) a compound having two or more polymerizable groups containing a C═C double bond, and (C) a cured film-forming composition containing a radical polymerization initiator,
0.1 parts by mass to 50 parts by mass of component (C) per 100 parts by mass of component (A), and substantially only component ( B) contains a polymerizable group containing a C=C double bond. A cured film-forming composition comprising:

(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 bonding group that 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 linking groups A, provided that the linking groups A or —CH ₂ —CH(OH)—CH ₂ —, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring (the divalent cyclic group is Any hydrogen atom on the cyclic group is a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxyl group having 1 to 3 carbon atoms, or a linear or branched chain. 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 optionally substituted with a fluorine atom),
Y ³ is 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 has 1 to 3 bonding groups can be interrupted by A, provided that the bonding groups A do not bond to each other.),
Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring (the divalent cyclic group is a linear or branched linear or branched alkyl group having 1 to 3 carbon atoms, 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 optionally substituted with a 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 such that any hydrogen atom on the cyclic group is linear or branched and has 1 carbon atom -3 alkyl groups, linear or branched alkoxyl groups of 1 to 3 carbon atoms, linear or branched fluorine-containing alkyl groups of 1 to 3 carbon atoms, linear or branched carbon 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 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 a fluorine-containing alkoxyl group having 1 to 18 carbon atoms (the Alkyl groups having 1 to 18 carbon atoms, fluorine-containing alkyl groups having 1 to 18 carbon atoms, alkoxyl groups having 1 to 18 carbon atoms and fluorine-containing alkoxyl groups having 1 to 18 carbon atoms are linear or branched. , or may be cyclic or a combination thereof, and may be interrupted by 1 to 3 linking groups A, provided that linking groups A are not linked 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 via a bonding group A,
When Y ³ and Y ⁴ represent a group other than a single bond, the bond between Y ³ and Y ⁴ may be a single bond or via a bonding group A,
When Y ⁴ and Y ⁵ represent a group other than a single bond, the bond between Y ⁴ and Y ⁵ may be a single bond or via a bonding group A,
When Y ⁵ and Y ⁶ represent a group other than a single bond, the bond between Y ⁵ and Y ⁶ may be a single bond or via a bonding group A,
When n is 2 or more, the bond between one Y ⁵ and its adjacent Y ⁵ may be a single bond or via a bonding group 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 formula [1] is 6-30. ). 2. The composition for forming a cured film according to claim 1, wherein the polymerizable group containing a C=C double bond of component (B) is at least one selected from an acrylic group, a methacrylic group, a vinyl group, an allyl group and a maleimide group. thing. 3. The cured film-forming composition according to claim 1, which contains 10 parts by mass to 2000 parts by mass of component (B) based on 100 parts by mass of component (A). An alignment material obtained by curing the cured film-forming composition according to any one of claims 1 to 3 . A retardation material characterized by being formed using a cured film obtained from the cured film-forming composition according to any one of claims 1 to 3 .