JP7070839B2 - Hardened film forming composition, alignment material and retardation material - Google Patents

Description

The present invention relates to a cured film-forming composition suitable for a vertically oriented material that orients liquid crystal molecules vertically. In particular, the present invention relates to a liquid crystal display (liquid crystal display) such as an IPS liquid crystal display (In-plane switching LCD) filled with a liquid crystal (Δε> 0) having a positive dielectric anisotropy. Useful for making + C plates (positive C plates) used to improve the viewing angle characteristics of LCDs) and the viewing angle characteristics of circular 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.

The IPS-LCD is characterized by a small change in brightness / color due to the viewing angle because the liquid crystal molecule does not tilt in the vertical direction, but its weaknesses are that it is difficult to increase the contrast ratio, brightness, and response speed. Be done. For example, as disclosed in Patent Document 1, the IPS-LCD in the early stage of the proposal does not use a viewing angle compensation film, and the IPS-LCD that does not use such a viewing angle compensation film has a tilt angle. Due to the relatively large light leakage in the dark state, it has the 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). In this document, the following configurations are shown for the liquid crystal display element described therein.
1) A liquid crystal layer having horizontal orientation is sandwiched between both substrates supplied by electrodes to which an electric field parallel to the liquid crystal layer surface can be applied.
2) One or more + A plate and + C plate 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) The phase difference value R _LC of the liquid crystal layer, the phase difference value R ₊ C of the + C plate, and the phase difference 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 in the thickness direction of the protective film of the polarizing plate is not shown (TAC, COP, PNB).

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

Japanese Unexamined Patent Publication No. 2-256023 Japanese Unexamined Patent Publication No. 11-133408 Japanese Unexamined Patent Publication No. 2009-122715 Japanese Unexamined Patent Publication No. 2001-281669 Japanese Unexamined Patent Publication No. 2015-79256

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

Further, in the vertically oriented film using polyimide which has been conventionally proposed, it is necessary to use a polyimide solvent such as N-methyl-2-pyrrolidone when producing the film. Therefore, there is no problem with a glass base material, but when the base material is a film, there is a problem that the base material is damaged when the alignment film is formed. In addition, the vertically oriented film using polyimide requires firing at a high temperature, and there is a problem that the film substrate cannot withstand the high temperature.
Further, a method of forming a vertically oriented film by directly treating the base material with a silane coupling agent having a long-chain alkyl has been proposed, but when the hydroxy group is not present on the surface of the base material, it 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 reduction in production cost, it has been required to be produced by so-called roll-to-roll on an inexpensive resin film such as a TAC (triacetyl cellulose) film and a COP (cycloolefin polymer) film. 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 demand for an alignment material having excellent adhesion and 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 thereof is that it has excellent vertical orientation, and also has the transparency and solvent resistance required for an optical compensation film. Further, a cured film for providing an alignment material having adhesion to a base material and a polymerizable liquid crystal layer and capable of stably orienting a polymerizable liquid crystal vertically even on a resin film under low temperature and short time firing conditions. Is to provide a forming composition.

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

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

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

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

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

As a second aspect, in the polymer of the component (A), the polymerizable group containing a C = C double bond is at least one selected from the group consisting of an acrylic group, a methacrylic group, a vinyl group, an allyl group and a maleimide group. The present invention relates to the cured film-forming composition according to the first aspect.
As a third aspect, the cured film formation according to the first or second aspect, further comprising (C) at least one selected from the group consisting of a monomer having a polymerizable group containing a C = C double bond and a polymer. Regarding the composition.
As a fourth aspect, the item according to any one of the first to third viewpoints, wherein the component (B) is contained in an amount of 0.1 part by mass to 50 parts by mass based on 100 parts by mass of the component (A). The present invention relates to a cured film forming composition.
As a fifth aspect, the cured film forming composition according to the third or fourth aspect, which contains 10 parts by mass to 1000 parts by mass of the component (C) based on 100 parts by mass of the component (A).

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

According to the first aspect of the present invention, in order to provide an alignment material having excellent vertical orientation and capable of stably vertically aligning a polymerizable liquid crystal even on a resin film under low temperature and short firing 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 having excellent vertical orientation and capable of stably vertically aligning a polymerizable liquid crystal 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 which can be formed on a resin film with high efficiency, has high transparency and high solvent resistance, and has adhesion to a substrate and a liquid crystal film.

<Cured film forming composition>
The cured film-forming composition of the present invention comprises a polymer having a vertically oriented group as a component (A) and a polymerizable group containing a C = C double bond, and a radical polymerization initiator as a component (B). contains. The cured film-forming composition of the present invention comprises a group consisting of a monomer and a polymer having a polymerizable group containing a C = C double bond as a component (C) in addition to the above components (A) and (B). It can also contain at least one selected from. Then, other additives can be contained as long as the effect of the present invention is not impaired.
The details of each component will be described below.

<Ingredient (A)>
The component (A) contained in the cured film-forming composition of the present invention is a polymer having a vertically oriented group and a polymerizable group containing a C = C double bond.
In the present specification, the vertically oriented group represents, for example, a group containing a hydrocarbon group having about 6 to 30 carbon atoms, and specifically, a group represented by the formula [1] described later.
Therefore, examples of the monomer having a vertically oriented group include a monomer having a hydrocarbon group having about 6 to 30 carbon atoms. Examples of the hydrocarbon group having 6 to 30 carbon atoms include a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms or a hydrocarbon group having 6 to 30 carbon atoms including an aromatic group. .. Therefore, specific examples of a monomer containing a hydrocarbon group having 6 to 30 carbon atoms include an alkyl ester of acrylic acid, an alkyl ester of methacrylic acid, an alkyl vinyl ether, 2-alkylstyrene, 3-alkylstyrene, and 4-alkylstyrene. N-alkylmaleimides in which the alkyl group has 6 to 30 carbon atoms, or the alkyl group of these monomers contains the above-mentioned aromatic group having 6 to 30 carbon atoms and has 6 to 6 carbon atoms. Examples thereof include those that have been replaced with 30 hydrocarbon groups.

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

In formula [1], Y ¹ represents a single bond or a binding group.
In the formula [1], Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms, or -CH ₂ -CH (OH) -CH _2- .
Further, as Y ² , a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle can be mentioned, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms and 1 carbon atom. It may be substituted with an alkoxyl group having 3 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.

Examples of the heterocycle include a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, a thiadiazole ring, a pyridazine ring, and a pyrazoline ring. Examples thereof include a triazine ring, a pyrazoline ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a cinnoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridin ring, which are more preferable. Is a pyrazole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazoline ring, a triazole ring, a pyrazine ring, and a 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 in the group mentioned as a specific example of the alkyl group. A group to which the atom -O- is bonded can be mentioned. Further, as the fluorine-containing alkyl group and the fluorine-containing alkoxyl group, a group in which any hydrogen atom of the alkyl group and the alkoxyl group is substituted with a fluorine atom can be mentioned.

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

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

The above-mentioned heterocycle, the alkyl group mentioned as the substituent, and the like can be the ones mentioned in the above-mentioned Y ² .

Further, Y ⁴ may be a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton. Preferred examples are cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, ergosteryl, estryl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, melatranil, methyltestrosteryl, noretisteryl, pregnenonyl, β-citosteryl, It is a divalent group having a structure in which two hydrogen atoms are removed from a structure selected from stigmasteryl, teststeryl, acetate cholesterol ester and the like. More specifically, for example, it is as follows.

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

In the formula [1], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups is a hydroxy group and has 1 to 3 carbon atoms. It may be substituted with an alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. The above-mentioned heterocycle, the alkyl group mentioned as the substituent, and the like can be the ones mentioned in the above ^- mentioned Y4.

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

Further, 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. Among them, n is preferably 0 to 3 from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.

In the 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 an alkoxyl group having 1 to 18 carbon atoms. Represents the fluorine-containing alkoxyl group of.

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. It is preferable to have. More preferably, Y ⁶ is an alkyl group having 1 to 17 carbon atoms or an alkoxyl group having 1 to 17 carbon atoms. Particularly preferably, Y ⁶ is an alkyl group having 1 to 16 carbon atoms or an alkoxyl group having 1 to 16 carbon atoms.

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

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

The alkyl group may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, or 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 can be mentioned.

Examples of the alkylene group include a divalent group obtained by removing one arbitrary hydrogen atom from the alkyl group.
Examples of the alkoxyl group include a group in which an oxygen atom —O— is bonded to a group mentioned as a specific example of the alkyl group.
Further, as the fluorine-containing alkyl group and the fluorine-containing alkoxyl group, a group in which any hydrogen atom of the alkyl group and the alkoxyl group is substituted with a fluorine atom can be mentioned.

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

Further, the alkylene group in Y ² and Y ³ and the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxyl group in Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. May be.

Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents -CH ₂ -CH (OH)-. When CH ₂ -represents, or Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent having the steroid skeleton. The organic group, the -CH ₂ -CH (OH) -CH _2- , the alkylene group, the alkyl group and the fluorine-containing alkyl group may be bonded to a group adjacent to them via a bonding group.

The above-mentioned linking groups are -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, and -O-CO-NH. Represents a group selected from the group consisting of-and-NH-CO-NH-.

In addition, a single bond represented by Y ² to Y ⁶ , an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocycle, a divalent organic group having a steroid skeleton, and -CH ₂ -CH ( OH) -CH _2- , an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. The total number of carbon atoms in the above is 6 to 30, for example, 6 to 20.
Of these, considering the vertical orientation and the coatability of the polymerizable liquid crystal, the vertically oriented group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 16.

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

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

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

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

The method for obtaining the polymer of the component (A) of the present invention is not particularly limited. For example, a polymer having a vertically oriented group and a specific functional group is produced in advance by a polymerization method such as radical polymerization. Next, a compound having a polymerizable group containing a C = C double bond and a group that reacts with the specific functional group (hereinafter referred to as a specific compound) can be reacted to obtain a polymer of the component (A). can.

As another method, a polymer containing a specific functional group, a compound having a group that reacts with the specific functional group and a vertically oriented group, a group that reacts with the specific functional group, and a C = C double bond are included in the polymerization. By reacting a compound having a sex group, the polymer of the component (A) can be obtained.

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

In the above-mentioned reaction with the specific functional group, the preferable combination of the specific functional group and the functional group of the specific compound and participating in the reaction is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, and a phenolic hydroxy. A group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride.

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

Hereinafter, specific examples of the monomer required to obtain the polymer having the above-mentioned specific functional group, that is, the specific monomer will be given. 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, N- (carboxyphenyl) acrylamide and the like.

Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethylmethacrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-. Epoxy-5-hexene and 1,7-octadienmonoepoxiside can be mentioned.

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

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

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

Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate and m-tetramethylxylene isocyanate.

Further, in the present invention, when a polymer having a specific functional group is obtained, in addition to the specific monomer, a monomer copolymerizable with the monomer and having no specific functional group can be used in combination.
Specific examples of such a monomer include an acrylic acid ester compound or a methacrylic acid ester compound having a structure different from that of the specific monomer, a maleimide compound, an acrylamide compound, an acrylonitrile, a maleic anhydride, a styrene compound, a vinyl compound and the like. ..

Hereinafter, specific examples of the above-mentioned monomers will be given, but the present invention is not limited thereto.
Examples of the acrylic acid ester compound having a structure different from that of the specific monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate and naphthyl acrylate. , Anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclo Examples thereof include decyl acrylate.

Examples of the methacrylic acid ester compound having a structure different from that of the specific monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate and naphthyl methacrylate. , Anthryl methacrylate, Anthrylmethyl methacrylate, Phenyl methacrylate, 2,2,2-Trifluoroethyl methacrylate, Cyclohexyl methacrylate, Isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, Tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecylmethacrylate, and 8-ethyl -8-Tricyclodecylmethacrylate and the like can be mentioned.

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

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

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

Further, as the polymer having the above-mentioned specific functional group, a commercially available product can be preferably used.
Specific examples of commercially available products of polymers having one or more epoxy groups at the side chains or ends are jER1001, 1002, 1003, 1004, 1055, 1007, 1009, as bisphenol A type epoxy resins. 1010, 834, 828 (above, manufactured by Mitsubishi Chemical Corporation), etc., and jER806, 807 (above, manufactured by Mitsubishi Chemical Corporation), etc. as bisphenol F type epoxy resins, and phenol novolac type epoxy. As the resin, jER152, 154 (above, manufactured by Mitsubishi Chemical Corporation), EPPN201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), etc., and as the cresol novolac type epoxy resin, ECN-1299 (Asahi Kasei). EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.), jER80S75 (manufactured by Mitsubishi Chemical Corporation) Etc., as a bisphenol A novolak type epoxy resin, jER157S70 (manufactured by Mitsubishi Chemical Corporation), etc., and as a polyol 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct, EHPE-3150 (Co., Ltd.). ) Made by Daicel) and the like.

Specific examples of commercially available polymers having one or more hydroxy groups at the side chains or ends include ADEKA-made Adecapolyesters P series, G series, EDP series, BPX series, FC series, and specific examples of polyether polyols. CM series, Uniox (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG -3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, Nonion (registered trademark) LT-221, ST-221, OT-221 and the like, and DIC as a specific example of the polyester polyol. Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD- X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD-X- 2560, Claret Polyester P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F-3010, P Specific examples of polycaprolactone polyols include -1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, C-590, C-1050, C-2050, C-2090, C-3090 and the like. Examples include DIC Polylite® OD-X-2155, OD-X-640, OD-X-2568, Daicel Chemical Praxel® 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like can be mentioned.

The polymer of the component (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 150,000, and preferably 3,000 to 100,000. Even more preferable. If the weight average molecular weight is more than 200,000 and is excessive, the solubility in a solvent may be lowered and the handleability may be lowered, and if the weight average molecular weight is less than 1,000 and too small, the light may be reduced. At the time of curing, the curing may be insufficient and the solvent resistance and heat resistance may decrease.
In the present specification, the weight average molecular weight is a value obtained by gel permission chromatography (GPC) using polystyrene as a standard sample.

The abundance ratio of the vertically oriented group in the polymer of the component (A) is preferably 3 mol% to 50 mol%, preferably 5 mol% to 45 mol%, per 100 mol of all repeating units of the polymer. Is even more preferable. If it is less than 3 mol%, the vertical orientation may be insufficient, and if it is more than 50 mol%, the adhesion to the liquid crystal display may be adversely affected.

The abundance ratio of the polymerizable group containing a C = C double bond in the polymer of the component (A) is preferably 20 mol% to 97 mol%, preferably 25 mol%, per 100 mol of all the repeating units of the polymer. It is more preferably ~ 95 mol%. If it is less than 20 mol%, curing may be insufficient, and if it is more than 97 mol%, vertical orientation may be insufficient.

<Ingredient (B)>
The component (B) in the cured film-forming composition of the present invention is a radical polymerization initiator.
Known radical polymerization initiators can be used, for example, alkylphenones, benzophenones, acylphosphine oxides, Michiller's benzoylbenzoates, oxime esters, tetramethylthium monosulfides, etc. Examples thereof include thioxanthones.

Examples of the radical polymerization initiator 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, Phenylphenones 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 Acetphenones such as -dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; quinones such as anthraquinone and 1,4-naphthoquinone. Classes; halogen compounds such as phenacylloride, tribromomethylphenylsulfone, tris (trichloromethyl) -s-triazine; [1,2'-bisimidazole] -3,3', 4,4'-tetraphenyl, [ 1,2'-bisimidazole] -1,2'-dichlorophenyl-3,3', 4,4'-bisimidazoles such as tetraphenyl, peroxides such as di-tert-butyl peroxide; 2,4 , 6-trimethylbenzoyldiphenylphosphine oxides and the like, acylphosphine oxides and the like.
Commercially available products include Irgacure 184, 369, 379EG, 651, 500, 907, CGI369, CG24-61, OXE02, Lucirin LR8728, Lucirin TPO, DaroCure 1116, 1173 (above, manufactured by BASF Corporation), Yubekrill P36 (UCB). It can be mentioned that it is commercially available under a trade name such as (manufactured by Co., Ltd.).

Among the above, 1- [2-methyl-4-methylthiophenyl] -2-morpholino-1-propanol, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one , Α, α-Dimethoxy-α-Phenylacetophenone and other acetophenones, phenasilcolide, tribromomethylphenylsulfone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2'-bisimidazoles and 4, Combination of 4'-bis (diethylamino) benzophenone and mercaptobenzothiazole, Lucillin TPO (trade name), Irgacure 651 (trade name), Irgacure 369 (trade name), Irgacure 907 (trade name), Irgacure OXE02 (trade name) Is preferable.

The radical polymerization initiator 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 be done. If the amount of the radical polymerization initiator used is less than the above range, it is easily affected by the deactivation of radicals due to oxygen (decrease in sensitivity), and if it is more than the above range, the compatibility is deteriorated and the storage stability is deteriorated. Tend to do.

<Ingredient (C)>
The cured film-forming composition of the present invention may contain at least one selected from the group consisting of a monomer having a polymerizable group containing a C = C double bond and a polymer as the component (C).

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. Further, the (meth) acryloyl group represents CH ₂ = CHCO− and CH (CH ₃ ) = CHCO−.

Hereinafter, as the monomer and polymer having a polymerizable group containing the component (C) component C = C double bond of the present invention, a polymerizable group containing a C = C double bond is contained in one molecule from the viewpoint of increasing the film strength. Monomers and polymers having two or more of them are preferable. Hereinafter, examples of suitable compounds will be given, but the component (C) 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. (Meta) 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 ( Meta) acrylate, 1,9-nonanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, pentaerythritol di (meth) Acrylate, Tricyclo [5.2.1.0 ^2,6 ] Decandimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy -1,3-di (meth) acryloyloxypropane, trishydroxyethylisocyanurate di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecylenoxy Examples thereof include ethylene glycol di (meth) acrylate, 1,3-adamantandiol di (meth) acrylate, 1,3-adamantan dimethanol di (meth) acrylate, and ethoxylated bisphenol A di (meth) acrylate.

As the compound having two or more (meth) acryloyl groups, commercially available products can be preferably used, for example, light acrylate 3EG-A, light acrylate 4EG-A, light acrylate 9EG-A, light acrylate 14EG-A, light acrylate PTMGA. -250, Ester NP-A, Ester MPD-A, Ester 1.6HX-A, Ester 1.9ND-A, Ester MOD-A, Ester DCP-A, Ester BP-4EAL, Light Acrylic BP-4PA, Light Ester HPP-A, Light Ester G-201P, Light Ester P-2M, Light Ester EG, Light Ester 2 EG, Light Ester 3 EG, Light Ester 4 EG, Light Ester 9 EG, Light Ester 14 EG, 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, AB1206PE, 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, same 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 Industry 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 of them are 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.]; Viscort # 195, # 230, # 260, # 310HP, # 335HP, # 700HV, # 540, # 802, # 295 [all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like.

Examples of the compound having three (meth) acryloyl groups (trifunctional compound) include ethylene oxide-modified 1,1,1-trimethylolethanetri (meth) acrylate [ethylene oxide-added moles 3 to 30] and ethylene oxide-modified trimethylol. Propanetri (meth) acrylate [ethylene oxide-added moles 3 to 30], propylene oxide-modified trimethylolpropanetri (meth) acrylate [propylene oxide-added moles 3 to 30], ethylene oxide-modified glycerintri (meth) acrylate [ethylene oxide-added moles] Numbers 3 to 30], propylene oxide-modified glycerintri (meth) acrylate [propylene oxide-added moles 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-trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, Examples thereof include pentaerythritol trimethylolpropane (meth) acrylate and glycerintri (meth) acrylate.

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

Examples of the compound having four (meth) acryloyl groups (tetrafunctional compound) include ethylene oxide-modified ditrimethylolpropanetetra (meth) acrylate [ethylene oxide-added moles 4 to 40] and ethylene oxide-modified pentaerythritol tetra (meth) acrylate [. Ethylene oxide addition mole number 4 to 40], ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like can be mentioned.

Commercially available products can be preferably used as the above-mentioned tetrafunctional compound, for example, NK ester ATM-4E and ATM-35E [all manufactured by Shin Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 40 [Dycel Ornex]. 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 above. Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 140, 1142, 180 [all of which are manufactured by Daicel Ornex Co., Ltd.] and the like.

Examples of the compound having 5 or more (meth) acryloyl groups (compound having 5 or more functions) include ethylene oxide-modified dipentaerythritol hexa (meth) acrylate [ethylene oxide-added molar number 6 to 60] and ethylene oxide-modified tripentaerythritol octa (meth). Examples thereof include meta) 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 preferably used for the above-mentioned compounds having five or more functionalities, for example, NK ester A-DPH-12E [manufactured by Shin Nakamura Chemical Industry Co., Ltd.], Viscort # 802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Acrylate DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9550, A-DPH [all manufactured by Shin Nakamura Chemical Industry Co., Ltd.]; DPHA [manufactured by Daicel Ornex Co., Ltd.], etc. Can be mentioned.

Examples of the bifunctional urethane (meth) acrylate include a urethane product of a (meth) acrylic acid adduct of phenylglycidyl ether and hexamethylene diisocyanate, and a urethane product of a (meth) acrylic acid adduct of phenylglycidyl ether and toluene diisocyanate. And so on.

As the above bifunctional urethane (meth) acrylate, commercially available products can be preferably used, for example, AH-600, AT-600 [all of which are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-2PPA, U-200PA, etc. UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-W2A [all manufactured by Shin Nakamura Chemical Industry 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 manufactured by Daicel Ornex Co., Ltd.]; Shikou (registered trademark) UV-6630B, 7000B, 7461TE, 2000B, 2750B, 3000, 3200B, 3210EA. , 3300B, 3310B, 3500BA, 3520TL, 3700B, 6640B [all of which are manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like.

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

Specific examples of commercially available products of 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 Dycel Ornex. Manufactured by Japan Co., Ltd.]; Shikou (registered trademark) UV-7650B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd.] and the like.

Examples of the polyfunctional urethane (meth) acrylate compound having five or more (meth) acryloyl groups (a urethane (meth) acrylate having five or more functions) include a urethane product of pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate. Examples thereof include urethanes of pentaerythritol tri (meth) acrylate and toluene diisocyanate, urethanates of pentaerythritol tri (meth) acrylate and isophorone diisocyanate, and urethanates of dipentaerythritol penta (meth) acrylate and hexamethylene diisocyanate. ..

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

The component (C) of the present invention may be a polymer compound having one or more side chains having a polymerizable unsaturated bond at the end in the molecule. Examples of the polymer compound having a side chain having a polymerizable unsaturated bond at the end include a polymer compound having a (meth) acryloyl group 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 type, epoxy acrylic type, and various (meth) acrylate type.

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

Examples of the compound as the component (C) include Acryt 8BR-930M, 8UH-1006, 8KQ-1001, 8KX-078, 1SX-1055 [all manufactured by Taisei Fine Chemical Co., Ltd.], SMP. Examples thereof include polymers such as -250A, SMP-360A, and SMP-550A [all manufactured by Kyoeisha Chemical Co., Ltd.].

When the component (C) is contained, the content is 10 parts by mass to 1000 parts by mass, preferably 15 parts by mass to 500 parts by mass, based on 100 parts by mass of the component (A).

<Solvent>
The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at that time may be such that the component (A), the component (B), the component (C) and / or other additives described later can be dissolved if necessary, and the type and structure thereof are particularly limited. Not.

Specific examples of the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like. 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. And so on.

When a cured film is formed on a resin film to produce an alignment material using the cured film-forming composition of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol are used. , 2-Heptanol, isobutylmethylketone, 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.

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

<Other additives>
Further, the cured film-forming composition of the present invention may be used as a sensitizer, an adhesion improver, a silane coupling agent, a surfactant, a rheology adjuster, a pigment, if necessary, as long as the effects of the present invention are not impaired. It can contain dyes, storage stabilizers, antifoaming agents, antioxidants and the like.

<Preparation of cured film forming composition>
The cured film-forming composition of the present invention contains a polymer having a vertically oriented group of the component (A) and a polymerizable group containing a C = C double bond, and a polymerization initiator of the component (B), if desired. (C) At least one selected from the group consisting of monomers and polymers having a polymerizable group containing a C = C double bond of the component, and further, other additives may be contained as long as the effects of the present invention are not impaired. It is a composition that can be produced. 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]: A cured film-forming composition containing 0.1 parts by mass to 50 parts by mass of the component (B) based on 100 parts by mass of the component (A) and the component (A).
[2]: Based on 100 parts by mass of the component (A) and (A), 0.1 parts by mass to 50 parts by mass of the component (B) and 10 parts by mass based on 100 parts by mass of the component (A). A cured film-forming composition containing 1000 parts by mass of the component (C) and a solvent.

The blending ratio, preparation method, etc. when the cured film-forming composition of the present invention is used as a solution will be described in detail below.
The proportion of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, preferably 2. It is by mass% to 50% by mass, more preferably 2% by mass to 20% by mass. Here, the solid content refers to a composition obtained by removing the solvent from all the components of the cured film forming composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, a method of mixing the component (B) and the component (C) in a predetermined ratio with a solution of the component (A) dissolved in a solvent to obtain a uniform solution, or this preparation method. At an appropriate stage of the above, there is a method of further adding and mixing other additives as needed.

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

<Hardened film, alignment material and retardation material>
The solution of the cured film forming composition of the present invention is applied to a substrate (for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, substrate coated with metal such as aluminum, molybdenum, chromium, etc., glass substrate, quartz substrate, ITO. Substrates, etc.) 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. A coating film is formed by applying bar coat, rotary coating, sink coating, roll coating, slit coating, rotary coating following the slit, inkjet coating, printing, etc. on a resin film such as a film). A cured film can be formed by heating and drying in a hot plate or an oven. The cured film can be applied as it is as an alignment material.

As a condition for heating and drying, the cross-linking reaction with a cross-linking agent may proceed to such an extent that the components of the cured film (aligning material) do not elute into the polymerizable liquid crystal solution applied thereto. For example, the temperature is 60 ° C. or higher. A heating temperature and 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 heating time are preferably 70 ° C. to 160 ° C., 0.5 minutes to 10 minutes.

The film thickness of the cured film (aligning material) formed by using the curable composition of the present invention is, for example, 0.05 μm to 5 μm, and is appropriately considered in consideration of the step of the substrate to be used and the 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 retardation material such as a polymerizable liquid crystal solution having vertical orientation is applied onto the alignment material. , Can be oriented on the alignment material. Then, by curing the retardation material in the oriented state as it is, the retardation material can be formed as a layer having optical anisotropy. When the substrate on which the alignment material is formed is a film, it is useful as a retardation film.

Further, using two substrates having the alignment material of the present invention formed as described above, the alignment materials on both substrates are bonded so as to face each other via a spacer, and then between the substrates. It is also possible to inject liquid crystal to form a liquid crystal display element in which the liquid crystal is oriented.
As described above, the cured film forming composition of the present invention can be suitably used for manufacturing various retardation materials (phase difference films), liquid crystal display elements and the like.

Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not limited thereto.
[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.

<Ingredients for component A>
LAA: Lauryl Acrylate PAA: Palmytyl Acrylate HEMA: 2-Hydroxyethyl Methacrylate GMA: Glycydyl Methacrylate AOI: Showa Denko Corporation Calends AOI
AIBN: α, α'-azobisisobutyronitrile LA: lauric acid M100: 3,4-epoxycyclohexylmethylmethacrylate 5PCA: 4- (4-pentylcyclohexyl) benzoic acid

<B component>
IRG: BASF IRGACURE 907
OXE: BASF IRGACURE OXE 02

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

<Others>
MAA: CYM303 methacrylic acid: Hexamethoxymethylmelamine PTSA: p-toluenesulfonic acid / monohydrate

<Solvent>
Each of the cured film-forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM), butyl acetate (BA), and ethyl acetate (EA) were used as the solvent.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Evaluation of adhesion]
Each of the cured film-forming compositions of Examples and Comparative Examples was applied onto a TAC film with a Wet film thickness of 4 μm using a bar coater. Each was heated and dried in a heat circulation oven at a temperature of 110 ° C. for 60 seconds, and then the coating film was exposed at 1000 mJ / cm ² to form a cured film on the TAC film.
On this cured film, a polymerizable liquid crystal solution for vertical orientation RMS03-015 manufactured by Merck Group Co., Ltd. was applied using a bar coater at a Wet thickness of 6 μm. The coating film on this substrate was exposed at 500 mJ / cm ² to prepare a retardation material.
The retardation material was cut with a cutter knife so as to have 5 × 5 squares at intervals of 1 mm in length and width. A cellophane tape peeling test was performed on this notch using scotch tape. In the evaluation, those that remained without peeling off all 25 squares were evaluated as ◯, and those that were peeled off even in 1 square were evaluated as x. The evaluation results are summarized in Table 3 later.

As shown in Table 3, the alignment material obtained by using the cured film-forming composition of Examples has good vertical orientation as well as the alignment material obtained by using the cured film-forming composition of Comparative Example. showed that.

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

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 and 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 circular polarizing plate used as an antireflection film for an IPS-LCD or an organic EL display.

Claims (6)

A vertically oriented material obtained from (A) a polymer having a vertically oriented group and a polymerizable group containing a C = C double bond, and (B) a cured film-forming composition containing a radical polymerization initiator.
A vertically oriented material obtained from a cured film-forming composition, wherein the vertically oriented group is a group represented by the following formula (1).

(In equation [1],
Y ¹ represents a single bond or a linking group
Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or -CH ₂ -CH (OH) -CH _2- , or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle. Represented, any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. It may be substituted with a fluorine-containing alkoxyl group or a fluorine atom of 3.
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms.
Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, or a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton. Any hydrogen atom on the cyclic group is a hydroxy group, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. It may be substituted with a fluorine-containing alkoxyl group or a fluorine atom of 3.
Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups is a hydroxy group, an alkyl group having 1 to 3 carbon atoms, or a carbon atom number. It may be substituted with an alkoxyl group of 1 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
n represents an integer from 0 to 4, and when n is 2 or more, 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. Represent,
The alkylene group in Y ² and Y ³ and the substituent on the cyclic group and the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxyl group in Y ⁶ are linear, branched or cyclic. Or a combination thereof,
Further, the alkylene group in Y ² and Y ³ and the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxyl group in Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. May,
Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents -CH ₂ -CH (OH) -CH. When ₂ -represents, or Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, a divalent organic having the steroid skeleton. The group, the -CH ₂ -CH (OH) -CH _2- , the alkylene group, the alkyl group and the fluorine-containing alkyl group may be bonded to a group adjacent to them via a bonding group.
The binding group is a group selected from the group consisting of -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH-. Represents
However, a single bond represented by Y ² to Y ⁶ , an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocycle, a divalent organic group having a steroid skeleton, and -CH ₂ -CH ( OH) -CH _2- , an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. The total number of carbon atoms in is 6 to 30). The polymer of the component (A), wherein the polymerizable group containing a C = C double bond is at least one selected from the group consisting of an acrylic group, a methacrylic group, a vinyl group, an allyl group and a maleimide group, according to claim 1. A vertically oriented material obtained from the cured film-forming composition described. (C) The vertically oriented material obtained from the cured film-forming composition according to claim 1 , further comprising at least one selected from the group consisting of a monomer having a polymerizable group containing a C = C double bond and a polymer. (A) Obtained from the cured film-forming composition according to any one of claims 1 to 3, which contains the component (B) of 0.1 parts by mass to 50 parts by mass based on 100 parts by mass of the component. Vertical alignment material to be. The vertically oriented material obtained from the cured film-forming assembly according to claim 3 or 4, which contains 10 parts by mass to 1000 parts by mass of the component (C) based on 100 parts by mass of the component (A). A retardation material, which is formed by using a vertically oriented material obtained from the cured film forming composition according to any one of claims 1 to 5.