KR20190103295A - Cured film formation composition, orientation material, and phase difference material - Google Patents

Abstract

(식 [1] 중, Y¹ 및 Y²는 단결합 등을 나타내고, Y³은 단결합 또는 탄소원자수 1~15의 알킬렌기를 나타내고, Y⁴는 단결합 또는 2가의 환상기 등을 나타내고, Y⁵는 벤젠환, 시클로헥산환 또는 복소환으로부터 선택되는 2가의 환상기를 나타내고, n은 0~4의 정수를 나타내고, n이 2 이상인 경우, Y⁵끼리는 동일할 수도 상이할 수도 있고, Y⁶은 수소원자 또는 탄소원자수 1~18의 알킬기 등을 나타낸다.)[PROBLEMS] To provide a cured film-forming composition for providing an alignment material having excellent vertical alignment and adhesion, capable of vertically aligning a polymerizable liquid crystal on a resin film with high sensitivity, and a phase difference material using such an alignment material.
[0011] 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, wherein the vertically oriented group is represented by the following formula (1) It is group displayed, The cured film formation composition characterized by the above-mentioned.

(In formula [1], Y <^1> and Y <^2> represent a single bond etc., Y <^3> represents a single bond or an alkylene group of 1-15 carbon atoms, Y <^4> represents a single bond or a bivalent cyclic group, etc., Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a hetero ring, n represents an integer of 0 to 4, and when n is 2 or more, Y ⁵ may be the same or different, and Y ⁶ Represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

Description

Cured film formation composition, orientation material, and phase difference material

This invention relates to the cured film formation composition suitable for the vertical alignment material which orientates a liquid crystal molecule perpendicularly | vertically. In particular, the present invention relates to a liquid crystal display (LCD) such as an IPS liquid crystal display (In-plane Switching LCD) filled with a liquid crystal (Δε> 0) having positive dielectric anisotropy. A cured film forming composition, an alignment material and a phase difference material useful for producing a + C plate (positive C plate), which are used to improve the viewing angle characteristic or the viewing angle characteristic of a circular polarizing plate used as an antireflection film of an organic EL display. will be.

IPS-LCD is characterized by low luminance change / color change due to the viewing angle because liquid crystal molecules are not inclined in the vertical direction. The weak point is that it is difficult to increase contrast ratio, luminance and response speed. For example, as disclosed in Patent Literature 1, in the IPS-LCD in the early stage of the proposal, a compensation film of the viewing angle is not used, and in the IPS-LCD without using such a compensation film of the viewing angle, in the dark state of the inclination angle. Due to the relatively large light leakage, there is a disadvantage in that it exhibits a low contrast ratio value.

Patent Document 2 discloses an IPS-LCD compensating film using a + C plate and a + A plate (positive A plate). In this document, the following constitution is shown about the liquid crystal display element described here.

1) A liquid crystal layer having a horizontal orientation is sandwiched between both substrates supplied by an electrode capable of applying an electric field parallel to the surface of the liquid crystal layer.

2) At least one + A plate and + C plate are inserted in both polarizers.

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 to satisfy the following equation.

R _LC : R _{+ C} : R _{+ A} ≒ 1: 0.5: 0.25

5) The relationship between the phase difference value of the protective film of a polarizing plate with respect to the phase difference value of + A plate and + C plate is not shown (TAC, COP, PNB).

In addition, the + A plate and the + C plate for the purpose of providing an IPS-LCD having high contrast characteristics and low color shift at the front and inclination angles by minimizing light leakage in the dark state at the inclination angle are provided. The IPS-LCD which has is disclosed (patent document 3). Furthermore, in order to improve the viewing angle characteristic of the circularly polarizing plate used as an antireflection film of an organic EL display, the proposal which uses + C plate is also made | formed (patent document 5).

Japanese Patent Application Laid-Open No. H2-256023 Japanese Patent Application Laid-Open No. H11-133408 Japanese Patent Publication No. 2009-122715 Japanese Patent Laid-Open No. 2001-281669 Japanese Patent Application Laid-Open No. 2015-79256

As conventionally proposed, the + C plate can compensate for light leakage at a large viewing angle of the polarizing plate, and thus is very useful as an optical compensation film of an IPS-LCD or a circular polarizing plate used as an antireflection film of an organic EL display. Do. However, in the conventionally known stretching method, it is difficult to express vertical alignment (positive C plate).

In addition, the vertical alignment film using the polyimide proposed conventionally needs to use the solvent of polyimides, such as N-methyl- 2-pyrrolidone, in preparation of a film | membrane. Therefore, it does not matter in the glass substrate, but when the substrate is a film, there is a problem that damage the substrate at the time of forming the alignment film. In addition, in the vertical alignment film using polyimide, baking at a high temperature is required, 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 the substrate with a silane coupling agent having a long chain alkyl or the like has also been proposed. However, when a hydroxyl group is not present on the surface of the substrate, the treatment is difficult and the substrate is limited. (Patent Document 4).

In recent years, production of so-called roll-to-roll is required on low-cost resin films such as TAC (triacetylcellulose) film and COP (cycloolefin polymer) film in accordance with the demand for reduction of manufacturing cost. However, in the alignment film formed from the conventional material as mentioned above, it was difficult to manufacture + C plate on a resin film.

Therefore, the alignment material which is excellent in adhesiveness and which can form highly reliable + C plate also on resin films, such as a TAC film, and the cured film formation composition for forming such an alignment material are calculated | required.

SUMMARY OF THE INVENTION The present invention has been made on the basis of the above findings and examination results. The problem to be solved is to have excellent vertical orientation and to have transparency and solvent resistance required for an optical compensation film, and to further improve the substrate and polymerizability. It is providing the cured film formation composition for providing the alignment material which has adhesiveness with a liquid crystal layer, and can also orientate a polymeric liquid crystal vertically stably under the baking conditions of low temperature short time also on a resin film.

In addition, another object of the present invention is obtained from the cured film-forming composition, has excellent vertical orientation and adhesiveness, has solvent resistance, and stably polymerizable liquid crystal on a resin film at low temperature and short time firing conditions. It is providing the orientation material which can be orientated perpendicularly | vertically, and the phase difference material useful for the + C plate formed using this orientation material.

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

In order to achieve the above object, the present inventors have conducted extensive studies to select a cured film-forming material based on a polymer having a vertical alignment group and a polymerizable group including a C = C double bond, thereby providing excellent vertical alignment and adhesion. It discovered that the cured film which has a thing can be formed, and completed this invention.

That is, the present invention is a first aspect,

(A) a polymer having a vertically oriented group and a polymerizable group containing a C = C double bond, and

(B) A cured film formation composition containing a radical polymerization initiator,

The said vertical orientation group is related with the cured film formation composition characterized by the group represented by following formula (1).

[Formula 1]

(In formula [1],

Y ¹ represents a single bond or a bonding 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 hetero ring, Any hydrogen atom on the cyclic group is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom May be,

Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,

Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having a steroid skeleton as 17 to 30 carbon atoms, and optionally Hydrogen atom may be substituted with 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, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom Maybe,

Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on these cyclic groups is a hydroxy group, an alkyl group having 1 to 3 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms May be substituted with 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 the integer of 0-4, and when n is 2 or more, Y <^5> may be same or different,

Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms,

The 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 either linear, branched or cyclic. Or a combination thereof,

In addition, the alkylene group for Y ² and Y ³ , and the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxyl group for Y ⁶ are interrupted by a bond of 1 to 3 unless the bonding groups are adjacent to each other. Maybe

Furthermore, 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 _2-. Or when Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having the steroid skeleton, the -CH ₂ -CH (OH) —CH ₂ —, this alkylene group, this alkyl group and this fluorine-containing alkyl group may be bonded via a group and a bonding group adjacent to these,

And the linking group represents a group selected from the group consisting of -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O-, and -NH-CO-NH-. ,

Provided that each of Y ² to Y ⁶ represents a single bond, 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, -CH ₂ -CH (OH ) -CH ₂ -, the sum of carbon atoms of 1 to 18 alkyl group, a carbon atom number of 1 to 18 fluorinated alkyl group, a carbon atom number of 1 to 18 carbon atoms and an alkoxyl group of 1 to 18 carbon atoms, a fluorine-containing alkoxyl group of the 6 ~ 30).

As a 2nd viewpoint, in the polymer of (A) component, the polymeric group containing C = C double bond is at least 1 sort (s) chosen from the group which consists of an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group. It relates to the cured film formation composition as described in a 1st viewpoint.

As a 3rd viewpoint, the cured film formation as described in a 1st viewpoint or a 2nd viewpoint which further contains at least 1 sort (s) chosen from the group which consists of a monomer and a polymer which have a polymerizable group containing a (C) C = C double bond. It relates to a composition.

As a 4th viewpoint, it is related with the cured film formation composition in any one of a 1st viewpoint thru | or a 3rd viewpoint which contains 0.1 mass part-50 mass parts (B) component based on 100 mass parts of (A) component. .

As a 5th viewpoint, based on 100 mass parts of (A) component, it is related with the cured film formation composition as described in a 3rd viewpoint or a 4th viewpoint containing 10 mass parts-1000 mass parts (C) component.

As a 6th viewpoint, it is obtained by hardening | curing the cured film formation composition in any one of a 1st viewpoint thru | or a 5th viewpoint, It is related with the orientation material characterized by the above-mentioned.

As a 7th viewpoint, it is formed using the cured film obtained from the cured film formation composition in any one of a 1st viewpoint thru | or a 5th viewpoint, It is related with the phase difference material characterized by the above-mentioned.

According to the first aspect of the present invention, there is provided a cured film-forming composition which has excellent vertical alignment and is useful for providing an alignment material capable of vertically aligning a polymerizable liquid crystal stably under low-temperature and short firing conditions even on a resin film. can do.

According to the second aspect of the present invention, it is possible to provide an alignment material having excellent vertical alignment and capable of stably vertically polymerizing the liquid crystal under low temperature and short firing conditions.

According to the third aspect of the present invention, a phase difference material which can be formed on a resin film with high efficiency and has high transparency and high solvent resistance and adhesion to a substrate and a liquid crystal film can be provided.

<Cured film forming composition>

The cured film formation composition of this invention contains the polymer which has a vertical orientation group which is (A) component, and a polymerizable group containing C = C double bond, and the radical polymerization initiator which is (B) component. In addition to the said (A) component and (B) component, the cured film formation composition of this invention is further selected from the group which consists of a monomer and polymer which have a polymeric group containing C = C double bond as (C) component. It may also contain at least one. And other additives can be contained as long as the effect of this invention is not impaired.

Hereinafter, the detail of each component is demonstrated.

<(A) component>

(A) component contained in the cured film formation composition of this invention is a polymer which has a polymerizable group containing a vertical orientation group and 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 Formula [1] described later.

Therefore, as a monomer which has a vertically oriented group, the monomer which has a hydrocarbon group of about 6-30 carbon atoms is mentioned, for example. Examples of the hydrocarbon group having 6 to 30 carbon atoms include a hydrocarbon group having 6 to 30 carbon atoms including a linear, branched or cyclic alkyl group having 6 to 30 carbon atoms or an aromatic group. Therefore, as a specific example of the monomer containing a C6-C30 hydrocarbon group, the alkyl ester of acrylic acid, the alkyl ester of methacrylic acid, the alkyl vinyl ether, 2-alkylstyrene, 3-alkylstyrene, 4-alkylstyrene, N Examples of the alkylmaleimide include those wherein the alkyl group has 6 to 30 carbon atoms, or the alkyl group of these monomers is substituted with a hydrocarbon group having 6 to 30 carbon atoms containing an aromatic group having 6 to 30 carbon atoms.

More specifically, the vertical alignment group is a group represented by the following formula [1].

[Formula 2]

In formula [1], Y <^1> represents a single bond or a bonding group.

Formula [1], Y ² is a single bond, carbon atom number of from 1 to 15 alkylene group or _{-CH 2 -CH (OH) -CH 2} - represents an.

Moreover, as Y <^2> , the bivalent cyclic group chosen from a benzene ring, a cyclohexane ring, or a heterocyclic ring is mentioned, Arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group and C1-C3 alkoxy It may be substituted by a real group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom.

Examples of the hetero 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 and pyri Diazine 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, oxadia A sol ring, an acridine ring, etc. are mentioned, More preferably, a pyrrole 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, Pyrazolidine ring, triazole ring, pyrazine ring, and benzimidazole ring.

Examples of the alkyl group mentioned as the substituent include methyl group, ethyl group, n-propyl group, isopropyl group and cyclopropyl group. As the alkoxyl group, oxygen atom-O- is added to the group mentioned as a specific example of the alkyl group. The combined group is mentioned. Examples of the fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group and alkoxyl group is substituted with a fluorine atom.

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

In said formula [1], Y <^3> represents a single bond or an alkylene group of 1-15 carbon atoms.

In said formula [1], Y <^4> represents a single bond or shows the bivalent cyclic group chosen from a benzene ring, a cyclohexane ring, or a heterocyclic ring, and the arbitrary hydrogen atoms on these cyclic groups are a hydroxyl group and a carbon atom number. It may be substituted with an alkyl group having 1 to 3, 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 heterocyclic group and the alkyl group mentioned as the substituent may be those mentioned for Y ² described above.

Further, as Y ⁴ , a divalent organic group having a steroid skeleton with 17 to 30 carbon atoms may be used. Preferred examples thereof are cholesteryl, andostereryl, β-cholesteryl, epiandrosteryl, erygosteryl, estryl, 11α-hydroxymethylsteryl, 11α-progesteryl, la Hydrogen atom from a structure selected from nosteryl, melatranyl, methyl testosteryl, norresteryl, pregnnonyl, β-sitosteryl, stigmasteryl, testosteryl, and cholesterol acetate, and the like. It is a bivalent group which has a structure which removed dog. More specifically, it is as follows, for example.

[Formula 3]

(Wherein * represents a bonding position)

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

In formula [1], Y <^5> represents the bivalent cyclic group chosen from a benzene ring, a cyclohexane ring, or a heterocyclic ring, and arbitrary hydrogen atoms on these cyclic groups are a hydroxyl group, an alkyl group of 1-3 carbon atoms, and a carbon atom number It may be substituted by the alkoxyl group of 1-3, the fluorine-containing alkyl group of 1-3 carbon atoms, the fluorine-containing alkoxyl group of 1-3 carbon atoms, or fluorine atom. The heterocyclic group and the alkyl group mentioned as the substituent may be those mentioned for Y ⁴ described above.

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

In addition, in formula [1], n represents the integer of 0-4, and when n is two or more, Y <^5> may be the same group or different group. Among these, 0-3 are preferable n from the point of availability of a raw material, and the ease of synthesis. More preferably, it is 0-2.

In formula [1], Y <^6> is a hydrogen atom, the C1-C18 alkyl group, the C1-C18 fluorine-containing alkyl group, the C1-C18 alkoxyl group, or the C1-C18 fluorine-containing alkoxyl group Indicates.

Among these, Y ⁶ is preferably 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. More preferably, Y ⁶ is an alkyl group having 1 to 17 carbon atoms or an alkoxyl group having 1 to 17 carbon atoms. Especially preferably, Y ⁶ is a C1-C16 alkyl group or a C1-C16 alkoxyl group.

On the other hand, 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 formula [1] may be any one of linear, branched, or cyclic or a combination thereof.

 The alkyl group 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-pent Tyl 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, etc. are mentioned. .

As said alkylene group, the bivalent group remove | excluding one arbitrary hydrogen atom from the said alkyl group is mentioned.

As said alkoxyl group, group which oxygen atom -O- couple | bonded with the group mentioned as a specific example of the said alkyl group is mentioned.

Examples of the fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group and alkoxyl group is substituted with a fluorine atom.

The alkylene group in Y ² and Y ³ , 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 may be linear, branched or cyclic. It may be one or a combination thereof.

In addition, the alkylene group in Y <^2> and Y <^3> , and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group in Y <^6> are interrupted by the coupling groups of 1-3 unless bond groups adjoin each other. It may be.

Furthermore, 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 _2- . Or when Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having the steroid skeleton, the -CH _2- CH (OH) —CH ₂ —, this alkylene group, this alkyl group and this fluorine-containing alkyl group may be bonded via a group adjacent to these and a bonding group.

In addition, the bond group is -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH- And -NH-CO-NH-.

On the other hand, Y ² to Y ⁶ each represent a single bond, 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, -CH ₂ -CH (OH ) -CH ₂ -, the sum of carbon atoms of 1 to 18 alkyl group, a carbon atom number of 1 to 18 fluorinated alkyl group, a carbon atom number of 1 to 18 carbon atoms and an alkoxyl group of 1 to 18 carbon atoms, a fluorine-containing alkoxyl group of the 6 -30, for example, 6-20.

Among these, in consideration of the vertical alignment property and the applicability of the polymerizable liquid crystal, the vertical alignment group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 16 carbon atoms.

In the polymer of (A) component, an acryl group, a methacryl group, a vinyl group, an allyl group, a maleimide group, etc. are mentioned as a polymeric group containing C = C double bond.

The polymerizable group including the C = C double bond may be incorporated into the side chain of the main skeleton of the polymer, that is, the specific side chain having the polymerizable group including the C═C double bond, and the side chain of the polymer of (A) component. It can be incorporated into.

In the polymer of (A) component, it is preferable that the specific side chain which has a polymeric group containing the said C = C double bond has 3-16 carbon atoms, and has an unsaturated bond at the terminal, Formula (b2) Particular preference is given to specific side chains represented by.

[Formula 4]

In formula (b2), R ⁵¹ is a divalent organic group selected from the group consisting of an aliphatic group containing 1 to 14 carbon atoms, an aliphatic group containing a cyclic structure, and an aromatic group, or a plurality of selected from this group. It is a bivalent organic group which consists of a combination of bivalent organic group. R ⁵¹ may contain an ester bond, an ether bond, an amide bond, a —CH ₂ CH (OH) CH ₂ — bond or a urethane bond.

In formula (b2), R ⁵² is a hydrogen atom or a methyl group, and the specific side chain which R ⁵² is a hydrogen atom is preferable, More preferably, it is a specific side chain whose terminal is an acryloyl group, a methacryloyl group, or a styryl group. .

The method of obtaining the polymer of (A) component of this invention is not specifically limited. For example, a polymer having a vertical alignment group and a specific functional group is produced by a polymerization method such as radical polymerization in advance. Subsequently, the polymer of (A) component can be obtained by making the compound which reacts with this specific functional group, and the compound (henceforth a specific compound) having a polymeric group containing a C = C double bond react.

As another method, a polymer having a specific functional group is reacted with a compound having a group and a vertical alignment group reacting with a specific functional group, a compound having a group reacting with a specific functional group and a polymerizable group including a C = C double bond. And the polymer of (A) component can be obtained.

Here, a specific functional group means functional groups, such as a carboxyl group, an epoxy group, a hydroxyl group, the amino group which has an active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or multiple types of functional group selected from these.

In reaction with the specific functional group mentioned above, the preferable combination of a specific functional group and group which participates in reaction as a functional group which a specific compound has is a carboxyl group, an epoxy group, a hydroxyl group, and an isocyanate group, a phenolic hydroxyl group, an epoxy group, and a carboxyl group Isocyanate group, an amino group, and an isocyanate group, or a hydroxyl group and an acid chloride.

In addition, the method of obtaining the polymer which has a specific functional group is not specifically limited. For example, a monomer having a functional group (specific functional group) for reacting with a specific compound, that is, a monomer having a carboxyl group, an epoxy group, a hydroxyl group, an amino group having active hydrogen, a phenolic hydroxyl group or an isocyanate group (specific monomer) It can be obtained by polymerization). Here, the monomer which has a specific functional group used for superposition | polymerization may be individual, and may use multiple types together if it is a combination which does not react during superposition | polymerization.

Below, the specific example of the monomer required to obtain the polymer which has said specific functional group, ie, a specific monomer, is 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, and mono- (2- (methacryloyloxy) ethyl) phthalate. , N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and the like.

As a monomer which has an epoxy group, glycidyl methacrylate, glycidyl acrylate, 3, 4- epoxycyclohexyl methyl methacrylate, allyl glycidyl ether, 3-ethenyl-7-oxa, for example Bicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.

As a monomer which has a hydroxy group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxy, for example. Butyl 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 Can be.

As a monomer which has an amino group, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned, for example.

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

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

In addition, in this invention, when obtaining the polymer which has a specific functional group, the monomer which can copolymerize with this monomer and does not have a specific functional group can be used together besides a specific monomer.

As an example of such a monomer, the acrylic acid ester compound or the methacrylic acid ester compound which have a structure different from a specific monomer, a maleimide compound, an acrylamide compound, an acrylonitrile, a maleic anhydride, a styrene compound, a vinyl compound, etc. are mentioned. Can be.

Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

As an acrylic acid ester compound which has a structure different from the said specific monomer, For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t -Butyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate Rate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy butyl acrylate, 2-methyl-2-adamantyl Acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate The can.

As methacrylic acid ester compound which has a structure different from the said specific monomer, For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate , Isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-tri Fluoroethyl 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, 8-ethyl-8- tricyclodecyl methacrylate, etc. are mentioned.

As said vinyl compound, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1, 2-epoxy-5-hexene, and 1,7-octadiene monoepoxide etc. are mentioned.

As said styrene compound, styrene, methyl styrene, chloro styrene, bromostyrene, etc. are mentioned, for example.

As said maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

Moreover, the polymer which has the said specific functional group can use a commercial item suitably.

As a specific example of the commercial item of the polymer which has one or more epoxy groups in a side chain or a terminal, As a bisphenol-A epoxy resin, jER1001, copper 1002, copper 1003, copper 1004, copper 1055, copper 1007, copper 1009, 1010, 834, 828 (above, made by Mitsubishi Chemical Co., Ltd.), etc. As a bisphenol F-type epoxy resin, jER806, 807 (above, made by Mitsubishi Chemical Co., Ltd.), etc., are phenol novolak type. Examples of the epoxy resin include jER152, copper 154 (above, manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, copper 202 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Asahi Kasei Co., Ltd., EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.), jER80S75 (Mitsubishi Chemical Co., Ltd. product) ) As a bisphenol A novolak-type epoxy resin, jER157S70 (made by Mitsubishi Chemical Corporation) etc. is mentioned as EHPE- as a 1, 2- epoxy- 4- (2- oxiranyl) cyclohexane addition product of a polyol. 3150 (made by Daicel Corporation) etc. are mentioned.

As a specific example of the commercial item of the polymer which has one or more hydroxyl groups in a side chain or a terminal, As a specific example of a polyether polyol, Adeka polyether P series, G series, EDP series, BPX series, FC series, CM by ADEKA Series, Nichi Oil 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® LT-221, ST-221, OT-221 and the like as specific examples 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, made by DIC OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD- X-2560, Kuraray polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F- 3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, C-590, C-1050, C-2050, C-2090, C-3090, etc. Spheres of Lactone Polyols Furnace 205, L205AL, 205U, 208, 210, 212 L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc. are mentioned.

It is preferable that the weight average molecular weights of the polymer of (A) component are 1,000-200,000, It is more preferable that it is 2,000-150,000, It is further more preferable that it is 3,000-100,000. If the weight average molecular weight is over 200,000, the solubility in the solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 1,000, the curing resistance may be insufficient at the time of photocuring, resulting in solvent resistance and Heat resistance may fall.

In addition, in this specification, a weight average molecular weight is a value obtained by using gel permeation chromatography (GPC) using polystyrene as a standard sample.

It is preferable that it is 3 mol%-50 mol% per 100 mol of all repeating units of this polymer, and, as for the polymer of (A) component, it is more preferable that they are 5 mol%-45 mol%. When it is less than 3 mol%, vertical orientation may become inadequate, and when it exceeds 50 mol%, it may adversely affect adhesiveness with a liquid crystal.

It is preferable that it is 20 mol%-97 mol% per 100 mol of total repeating units of this polymer in the polymer of (A) component, and the abundance rate of the polymeric group containing C = C double bond is 25 mol%-95 mol It is more preferable that it is%. When it is less than 20 mol%, hardening may become inadequate, and when it is excessive than 97 mol%, vertical orientation may become inadequate.

<(B) component>

(B) component in the cured film formation composition of this invention is a radical polymerization initiator.

As a radical polymerization initiator, a well-known thing can be used, For example, alkyl phenones, benzophenones, acyl phosphine oxides, Michler's benzoyl benzoate, oxime ester, tetramethyl thiuram mono Sulfides, thioxanthones and the like.

As a radical polymerization initiator used by this invention, For example, alpha-diketones, such as diacetyl; Acyl phosphorus such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) Benzophenones such as 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-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino-1- ( Acetophenones such as 4-morpholinophenyl) -butan-1-one; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, and tris (trichloromethyl) -s-triazine; [1,2'-bisimidazole] -3,3 ', 4,4'-tetraphenyl, [1,2'-bisimidazole] -1,2'-dichlorophenyl-3,3', 4, Peroxides, such as bisimidazoles, such as 4'- tetraphenyl, and di-tert- butyl peroxide; And acyl phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

As a commercial item, Igacure 184, 369, 379EG, 651, 500, 907, CGI369, CG24-61, OXE02, Lucirin LR8728, Lucirin TPO, Tarocure 1116, 1173 (more, product made in BASF Corporation), Yube What is marketed by brand names, such as a krill P36 (made by UCB Corporation), are mentioned.

Among the above, 1- [2-methyl-4-methylthiophenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- Acetophenones such as 1-one, α, α-dimethoxy-α-phenylacetophenone, phenacyl chloride, tribromomethylphenylsulfone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2 ' Combination of -bisimidazole with 4,4'-bis (diethylamino) benzophenone and mercapto benzothiazole, Lucirin TPO (brand name), Igacure 651 (brand name), Igacure 369 (brand name), Igacure 907 (brand name) and Igacure OXE02 (brand name) are preferable.

The radical polymerization initiators may be used alone, or may be used in combination of two or more thereof.

The radical polymerization initiator is preferably 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). When the amount of the radical polymerization initiator used is less than the above range, it is easy to be affected by the deactivation of the radicals due to oxygen (decrease in sensitivity). When the radical polymerization initiator is more than the above range, the compatibility tends to be poor and the storage stability tends to decrease.

<(C) component>

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

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

Hereinafter, as a monomer and a polymer which have a polymeric group containing (C) component C = C double bond of this invention, from a viewpoint of raising a film strength, two polymerizable groups containing C = C double bond are contained in 1 molecule. The monomer and polymer which have the above are preferable. Hereinafter, although the example of a suitable compound is given, (C) component is not limited to these illustrations.

As a compound which has two (meth) acryloyl groups, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 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 glycoldi (Meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, 2-methyl-1,8-octanedioldi (meth) acrylate, 1 , 10-decanedioldi (meth) acrylate, pentaerythritoldi (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanedimethanoldi (meth) acrylate, dioxane glycoldi (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) acrylo Iloxyethoxy) phenyl] fluorene, undecyleneoxyethylene glycol di (meth) acrylate, 1,3-adamantanedioldi (meth) acrylate, 1,3-adamantanedimethanoldi (meth) acrylic Ethoxylated bisphenol A di (meth) acrylate etc. are mentioned.

The compound which has two or more (meth) acryloyl groups can use a commercial item suitably, For example, light acrylate 3EG-A, light acrylate 4EG-A, light acrylate 9EG-A, light acrylate 14EG-A, Lightacrylate PTMGA-250, Lightacrylate NP-A, Lightacrylate MPD-A, Lightacrylate 1.6HX-A, Lightacrylate 1.9ND-A, Lightacrylate MOD-A, Lightacryl Light 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 Hotel's G-201P, Light Ester BP-2EMK [above, both the Tokyo Ischia Chemical (Co., Ltd.); NK ester 701A, copper A-200, copper A-400, copper A-600, copper A-1000, copper A-B1206PE, copper ABE-300, copper A-BPE-10, copper A-BPE-20, copper A -BPE-30, A-BPE-4, A-BPEF, A-BPP-3, A-DCP, A-DOD-N, A-HD-N, A-NOD-N, East APG-100, East APG-200, East APG-400, East APG-700, East A-PTMG-65, East 1G, East 2G, East 3G, East 4G, East 9G, East 14G, East 23G, East BPE -80N, copper BPE-100, copper BPE-200, copper BPE-500, copper BPE-900, copper BPE-1300N, copper DCP, copper DCP-N, copper HD-N, copper NOD-N, copper NPG, copper 1206PE, copper 701, copper 9PG (above, all manufactured by Shin-Nakamura Chemical Co., Ltd.); FANCRYL FA-124AS, East FA-129AS, East FA-222A, East FA-240A, East FA-P240A, East FA-P270A, East FA-321A, East FA-324A, East FA-PTG9A, East FA-121M, East FA-124M, East FA-125M, East FA-220M, East FA-240M, East FA-320M, East FA-321M, East FA-3218M, East FA-PTG9M [above, all made by Hitachi Chemical Co., Ltd.] ; DPGDA, HODA, TPGDA, EBECRYL® 145, Iso 150, IRR214-K, PEG400DA-D, EBECRYL® 11, HPDNA [manufactured by Daicelolnex Corporation]; Biscot # 195, East # 230, East # 260, East # 310HP, East # 335HP, East # 700HV, East # 540, East # 802, East # 295 [above, all manufactured by Japan Synthetic Chemical Industries, Ltd.], etc. Can be mentioned.

As a compound (trifunctional compound) which has three (meth) acryloyl groups, For example, ethylene oxide modified 1,1,1- trimethylol ethane tri (meth) acrylate [the number of ethylene oxide addition moles 3-30], Ethylene oxide modified trimethylol propane tri (meth) acrylate [ethylene oxide added mole number 3-30], propylene oxide modified trimethylol propane tri (meth) acrylate [propylene oxide added mole number 3-30], ethylene oxide modified glycerin tree ( Meth) acrylate [ethylene oxide addition mole number 3-30], propylene oxide modified glycerin tri (meth) acrylate [propylene oxide addition mole number 3-30], tris (2- (acryloyloxy) ethyl) isocyanurate (epsilon) -caprolactone modified tris (2- (acryloyloxy) ethyl) isocyanurate [ε-caprolactone addition mole number 1-30], 1,1,1- trimethylol ethane tri (meth) acrylate, Trimethylolpropane tree ( Agent) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin tri (meth) acrylate.

As the said trifunctional compound, a commercial item can be used suitably, For example, Biscoat # 360 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; NK ester A-GLY-9E, copper A-GLY-20E, and AT-20E (above, all made by Shin-Nakamura Chemical Co., Ltd.); TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [above, all manufactured by Daicel Allnex Co., Ltd.], biscot # 295, east # 300 [more, all manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Light acrylate TMP-A, copper PE-3A, light ester TMP (above, all manufactured by Kyoeisha Chemical Co., Ltd.); NK ester A-9300, copper A-9300-1CL, copper A-TMM-3, copper A-TMM-3L, copper A-TMM-3LM-N, copper A-TMPT, copper TMPT [above, all Shinnakamura Chemical Industrial Co., Ltd. product; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 (all are manufactured by Daicel Allnex Co., Ltd.), etc. are mentioned.

As a compound (4-functional compound) which has four (meth) acryloyl groups, For example, ethylene oxide modified ditrimethylol propane tetra (meth) acrylate [the number of ethylene oxide addition moles 4-40], ethylene oxide modified pentaerythritol Tetra (meth) acrylate [the number of ethylene oxide added moles 4-40], ditrimethylol propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. are mentioned.

As said tetrafunctional compound, a commercial item can be used suitably, For example, NK ester ATM-4E and the same ATM-35E (all are the Shin-Nakamura Chemical Co., Ltd. product); Biscot # 300 [manufactured by Osaka Organic Chemical Industry Co., Ltd.] such as EBECRYL (registered trademark) 40 [manufactured by Daicel Allnex Co., Ltd.]; Light acrylate PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK ester AD-TMP and copper A-TMMT (above, all made by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (trademark) 140, 1142, 180 (above, all are manufactured by Daicel All-Nex Corporation), etc. are mentioned.

As a compound (5-functional or more functional compound) which has five or more (meth) acryloyl groups, For example, ethylene oxide modified dipentaerythritol hexa (meth) acrylate [the number of ethylene oxide addition moles 6-60], ethylene oxide modified tree Pentaerythritol octa (meth) acrylate [ethylene oxide addition mole number 6-60], dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, etc. are mentioned. Can be.

A commercially available product can be used suitably for the said 5-functional or more compound, For example, NK ester A-DPH-12E [made by Shin-Nakamura Chemical Co., Ltd.], bis coat # 802 [manufactured by Osaka Organic Chemical Co., Ltd.] ; Light acrylate DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK ester A-9550, copper A-DPH (above, all made by Shin-Nakamura Chemical Co., Ltd.); DPHA (made by Daicel Allnex Co., Ltd.) etc. are mentioned.

As a bifunctional urethane (meth) acrylate, the urethane compound of the (meth) acrylic acid addition product of phenylglycidyl ether, and hexamethylene diisocyanate, the (meth) acrylic acid addition product of phenylglycidyl ether, And urethane compounds with toluene diisocyanate.

As said bifunctional urethane (meth) acrylate, a commercial item can be used suitably, For example, AH-600 and AT-600 (all are the Kyoeisha Chemical Co., Ltd. product or more); NK Oligo U-2PPA, East U-200PA, East UA-160TM, East UA-290TM, East UA-4200, East UA-4400, East UA-122P, East UA-W2A [above, all Shinnakamura Chemical Co., Ltd. )My]; EBECRYL (trademark) 210, 215, 230, 244, 244, 245, 270, 280 / 15IB, 284, 285, 4858, 8830, 8402, 8402, 8411, 8804, 88807 , 9227EA, 9270, KRM (registered trademark) 7735 (above, all manufactured by Daicel Allnex Co., Ltd.); Shiko (trademark) UV-6630B, copper 7000B, copper 7461TE, copper 2000B, copper 2750B, copper 3000, copper 3200B, copper 3210EA, copper 3300B, copper 3310B, copper 3500BA, copper 3520TL, copper 3700B, copper 6640B And Japan Synthetic Chemical Co., Ltd.].

As a specific example of the commercial item of the polyfunctional urethane (meth) acrylate compound which has three (meth) acryloyl groups, NK oligo UA-7100 [made by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (trademark) 204, east 205, east 264, east 265, east 294 / 25HD, east 1259, east 4820, east 8311, east 8465, east 8701, east 9260, KRM (registered trademark) 8296, east 8667 , All are manufactured by Daicel Allnex Co., Ltd .; Shiko (trademark) UV-7550B, 7000B, 7510B, 7461TE, 2750B (all are manufactured by Nippon Synthetic Chemical Co., Ltd.) and the like.

As a specific example of the commercial item of the polyfunctional urethane (meth) acrylate compound which has four (meth) acryloyl groups, EBECRYL (trademark) 8210, 8405, KRM (registered trademark) 8528 [above, all are Disselolnex (subject]; Shiko (trademark) UV-7650B (made by Japan Synthetic Chemical Co., Ltd.), etc. are mentioned.

As a polyfunctional urethane (meth) acrylate compound (five functional or more urethane (meth) acrylate) which has five or more (meth) acryloyl groups, for example, pentaerythritol tri (meth) acrylate and hexamethylene diisocyanate Urethanes with pentaerythritol tri (meth) acrylate and toluene diisocyanate, urethanes with pentaerythritol tri (meth) acrylate and isophorone diisocyanate, dipentaerythritol penta (meth) acrylate And urethane compounds with hexamethylene diisocyanate.

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

The (C) component of this invention may be a high molecular compound which has one or more side chains whose terminal is a polymerizable unsaturated bond in a molecule | numerator. As a high molecular compound which has a side chain whose terminal is a polymerizable unsaturated bond, Preferably, the high molecular compound which has a (meth) acryloyl group in two or more side chains in a molecule | numerator is mentioned.

As said high molecular compound, the high molecular compound containing one or more (meth) acryloyl groups, such as a urethane acryl type, an epoxy acryl type, and various (meth) acrylate type, is mentioned.

The weight average molecular weight of the high molecular compound of (C) component becomes like this. Preferably it is 1,000-200,000, More preferably, it is 5,000-50,000. When molecular weight is less than 1,000, the effect of this invention may not be exhibited. On the other hand, when molecular weight exceeds 100,000, it may not melt | dissolve in a composition.

As a compound which is such (C) component, For example, Acrite 8BR-930M, 8UH-1006, 8KQ-2001, 8KX-078, 1SX-1055 [more than Daisei Fine Chemical Co., Ltd. product], And polymers such as SMP-250A, SMP-360A, and SMP-550A (above, manufactured by Kyoeisha Chemical Co., Ltd.).

Content in the case of containing (C) component is 10 mass parts-1000 mass parts based on 100 mass parts of (A) component, Preferably they are 15 mass parts-500 mass parts.

<Solvent>

The cured film formation composition of this invention is mainly used in the solution state melt | dissolved in the solvent. The solvent used at this time should just melt | dissolve (A) component, (B) component, (C) component and / or the other additive mentioned later as needed, and the kind, structure, etc. are not specifically limited.

As a specific example of a solvent, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1- butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl 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-pentane On, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate Ethyl hydroxy acetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, pyruvic acid Ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentylmethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like. .

When using the cured film formation composition of this invention, a cured film is formed on a resin film and an orientation material is manufactured, 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, etc. are preferable at the point that a resin film is a solvent which shows tolerance.

These solvents can be used individually by 1 type or in combination of 2 or more types.

<Other additives>

Furthermore, as long as the effect of this invention is not impaired, the cured film formation composition of this invention is a sensitizer, an adhesion promoter, a silane coupling agent, surfactant, a rheology regulator, a pigment, dye, a storage stabilizer, an antifoamer. And antioxidants.

<Preparation of the cured film forming composition>

The cured film formation composition of this invention contains the polymer which has a vertical orientation group of (A) component, and a polymerizable group containing C = C double bond, and the polymerization initiator of (B) component, and if necessary, It is a composition which can contain at least 1 sort (s) chosen from the group which consists of a monomer and a polymer which have a polymerizable group containing C = C double bond, and the other additive, unless the effect of this invention is impaired. And usually, they are used as a form of the solution which melt | dissolved in the solvent.

The preferable example of the cured film formation composition of this invention is as follows.

[1]: Cured film formation composition containing 0.1 mass part-50 mass parts (B) component based on (A) component and 100 mass parts of (A) component.

[2]: 10 parts by mass to 1000 parts by mass based on (B) component and 100 parts by mass of (A) component based on (A) component and 100 parts by mass of component (A) (C) component and the cured film formation composition containing a solvent.

The compounding ratio, preparation method, etc. at the time of using the cured film formation composition of this invention as a solution are explained in full detail below.

Although the ratio of solid content in the cured film formation composition of this invention is not specifically limited as long as each component is melt | dissolving uniformly in a solvent, It is 1 mass%-60 mass%, Preferably it is 2 mass%-50 It is mass%, More preferably, it is 2 mass%-20 mass%. Here, solid content means what remove | excluding the solvent from all the components of a cured film formation composition.

The preparation method of the cured film formation composition of this invention is not specifically limited. As a preparation method, for example, the method of mixing (B) component, Furthermore, (C) component etc. to the solution of (A) component melt | dissolved in a solvent in a predetermined ratio, and to make it a uniform solution, or this preparation method In the appropriate step of, there may be mentioned a method of further adding and mixing other additives as necessary.

Moreover, it is preferable to use the prepared solution of the cured film formation composition, after filtering using a filter etc. which are about 0.2 micrometer in pore diameter.

<Cured film, alignment material, and phase difference material>

The solution of the cured film-forming composition of the present invention may be a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc., a glass substrate, or a quartz substrate). , ITO substrate, etc.) or a film substrate (for example, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET)) A film, acrylic film, resin film such as polyethylene film), etc., by coating with a bar coat, rotary coating, shedding coating, roll coating, slit coating, slit followed by rotary coating, inkjet coating, printing, etc. Then, the cured film can be formed by heat-drying in a hotplate, oven, etc. This cured film can be applied as an orientation material as it is.

As conditions for heat drying, the crosslinking reaction by a crosslinking agent should just advance so that the component of a cured film (orientation material) may not elute in the polymeric liquid crystal solution apply | coated on it, for example, temperature 60 degreeC-200 The heating temperature and heating time suitably selected from the range of 0, C and 0.4 minutes-60 minutes are employ | adopted. Heating temperature and heating time become like this. Preferably they are 70 degreeC-160 degreeC, and 0.5 minute-10 minutes.

The film thickness of the cured film (alignment material) formed using the curable composition of this invention is 0.05 micrometer-5 micrometers, for example, and can select suitably in consideration of the level | step difference of the board | substrate to be used, and the optical and electrical property.

Since the orientation material formed from the cured film composition of this invention has solvent resistance and heat resistance, retardation materials, such as the polymeric liquid crystal solution which has a vertical orientation, can be apply | coated on this orientation material, and it can orientate on an orientation material. And the phase difference material can be formed as a layer which has optical anisotropy by hardening the phase difference material which became the orientation state as it is. And when the board | substrate which forms an orientation material is a film, it becomes useful as a retardation film.

In addition, by using two substrates having the alignment member of the present invention formed as described above, and pasting the alignment members on both substrates to face each other via a spacer, the liquid crystal is injected between these substrates to form a liquid crystal. It can also be set as an oriented liquid crystal display element.

Thus, the cured film formation composition of this invention can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.

Example

Hereinafter, although an Example of this invention is given and this invention is demonstrated concretely, this invention is not limited to these and is interpreted.

[Abbreviated sign used in the embodiment]

The meanings of the abbreviations used in the following examples are as follows.

<Raw material of component A>

LAA: Laurylacrylate

PAA: Palmitylacrylate

HEMA: 2-hydroxyethyl methacrylate

GMA: glycidyl methacrylate

Aoi: car lens AOI made by Showa Denko

AIBN: α, α'-azobisisobutyronitrile

LA: lauryl acid

M100: 3,4-epoxycyclohexylmethyl methacrylate

5PCA: 4- (4-pentylcyclohexyl) benzoic acid

<Component B>

IRG: IRGACURE 907 made by BASF Corporation

OXE: IRGACURE OXE 02 made by BASF Corporation

<C component>

DPha: dipentaerythritol hexaacrylate made by Daicel Allnex Co., Ltd.

SMP: UV curing type acrylic polymer SMP-550A manufactured by Kyisha Chemical Co., Ltd.

<Others>

MAA: methacrylic acid

CYM303: Hexamethoxymethylmelamine

PTSA: p-toluenesulfonic acid monohydrate

<Solvent>

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

<Measurement of molecular weight of polymer>

The molecular weight of the acrylic copolymer in the polymerization example is as follows using the room temperature gel permeation chromatography (GPC) apparatus (GPC-101) by Shodex Corporation, and the column (KD-803, KD-805) by Shodex Corporation. It was measured by.

In addition, the following number average molecular weight (henceforth Mn) and a weight average molecular weight (henceforth Mw) were shown by polystyrene conversion value.

Column temperature: 50 ℃

Eluent: N, N-dimethylformamide (as additive, lithium bromide monohydrate (LiBr.H ₂ O) is 30 mmol / L, phosphoric acid anhydrous crystal (o-phosphate) is 30 mmol / L, tetrahydrofuran (THF) 10 mL / L)

Flow rate: 1.0mL / min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) by Tosoh Corporation, and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) by Polymer Laboratories.

<Polymerization Example 1>

An acrylic copolymer solution was obtained by dissolving AIBN 0.3g in PM 45.7g as LAA 3.0g, GMA 12.0g, and a polymerization catalyst and reacting at 80 ° C for 20 hours. The obtained acrylic copolymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P1) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic copolymer was 14,000 and Mw was 38,000.

<Polymerization Example 2>

An acrylic copolymer solution was obtained by dissolving AIBN 0.3g in PM 45.7g as PAA 3.0g, GMA 12.0g, and a polymerization catalyst, and reacting at 80 degreeC for 20 hours. The obtained acrylic copolymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P2) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic copolymer was 12,000 and Mw was 30,000.

<Polymerization Example 3>

An acrylic copolymer solution was obtained by dissolving 0.3 g of AIBN in 45.7 g of PM as LAA 3.0 g, HEMA 12.0 g, and a polymerization catalyst, and reacting at 80 ° C. for 20 hours. The obtained acrylic copolymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, and the acrylic copolymer (P3) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic copolymer was 8,600 and Mw was 20,000.

<Polymerization Example 4>

An acrylic copolymer solution was obtained by dissolving 0.3 g of AIBN in 45.7 g of PM as LAA 1.5 g, GMA 13.5 g, and a polymerization catalyst, 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 acrylic copolymer (P4) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic copolymer was 15,000 and Mw was 32,000.

<Polymerization Example 5>

An acrylic copolymer solution was obtained by dissolving AIBN 0.3g in PM 45.7g as LAA 4.5g, GMA 10.5g, and a polymerization catalyst, 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 acrylic copolymer (P5) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic copolymer was 14,000 and Mw was 31,000.

<Polymerization Example 6>

An acrylic copolymer solution was obtained by dissolving 0.4 g of AIBN in 46.4 g of PM as 10.0 g of M100 and a polymerization catalyst 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 acrylic copolymer (P6) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic copolymer was 18,000 and Mw was 38,000.

<Polymerization Example 7>

The acrylic copolymer solution (solid content concentration of 25 mass%) (P7) was obtained by melt | dissolving AIBN0.68g in PM107.0g as MAA 13.8g, LAA 14.1g, HEMA 7.2g, and a polymerization catalyst, and making it react at 80 degreeC for 16 hours. Mn of the obtained acrylic copolymer was 13,300 and Mw was 27,800.

Synthesis Example 1

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

Synthesis Example 2

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

Synthesis Example 3

2.0 g of 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 were dissolved in 60 g of tetrahydrofuran as a reaction catalyst. It was made to react at 60 degreeC for 5 hours. This solution was slowly added dropwise to 500 g of hexane to precipitate a solid, and filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-3) having an acroyl group. ^It was confirmed by ¹ H-NMR analysis that the acrylic copolymer (PA-3) had an acroyl group.

Synthesis Example 4

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

Synthesis Example 5

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

Synthesis Example 6

8.0 g of 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, at 110 ° C. The reaction was carried out for 20 hours. This solution was slowly added dropwise to 500 g of hexane to precipitate a solid, and filtered and dried under reduced pressure to obtain an acrylic copolymer (PA-6) having an acroyl group. ¹ H-NMR analysis was conducted to confirm that the acrylic copolymer (PA-6) had an acroyl group.

Synthesis Example 7

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

Synthesis Example 8

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

<Example>

Each cured film formation composition of an Example was prepared with the composition shown in Table 1. Next, the cured film was formed using each cured film formation composition, and the vertical orientation and adhesiveness were evaluated about each obtained cured film.

TABLE 1

Comparative Example

Each cured film formation composition of the comparative example shown in Table 2 was prepared with reference to the method of WO2015 / 019962. Next, the cured film was formed using each cured film formation composition, and the vertical orientation and adhesiveness were evaluated about each obtained cured film.

[Evaluation of Vertical Orientation]

Each cured film formation composition of an Example was apply | coated on the TAC film by 4 micrometers of Wet film thickness using the bar coater. Heat-drying was performed in a thermocyclic oven for 60 second at the temperature of 110 degreeC, respectively, Then, this coating film was exposed at 1000mJ / cm <^2>, and the cured film was formed on TAC film, respectively.

On this cured film, the polymer liquid crystal solution RMS03-015 made by Merck Co., Ltd. was apply | coated to Wet film thickness of 6 micrometers using the bar coater. This coating film was exposed at 500mJ / cm <^2> , and the phase difference material was produced.

Using these manufactured phase difference materials, the incidence angle dependence of the in-plane phase difference was measured using OTSKA Electronics Co., Ltd. phase difference measuring device RETS100. It was determined that the in-plane phase difference value at the incident angle of 0 degrees was 0 and the in-plane phase difference at the incident angle of ± 50 degrees was in the range of 38 ± 5 nm. The evaluation results are summarized in Table 3 later.

Each cured film formation composition of a comparative example was apply | coated on the TAC film by 4 micrometers of Wet film thickness using the bar coater. Heat-drying was performed in a thermocyclic oven for 60 second at the temperature of 110 degreeC, respectively, and the cured film was formed on TAC film, respectively.

On this cured film, the polymer liquid crystal solution RMS03-015 made by Merck Co., Ltd. was apply | coated to Wet film thickness of 6 micrometers using the bar coater. This coating film was exposed at 500mJ / cm <^2> , and the phase difference material was produced.

Using these manufactured phase difference materials, the incidence angle dependence of the in-plane phase difference was measured using OTSKA Electronics Co., Ltd. phase difference measuring device RETS100. It was determined that the in-plane phase difference value at the incident angle of 0 degrees was 0 and the in-plane phase difference at the incident angle of ± 50 degrees was in the range of 38 ± 5 nm. The evaluation results are summarized in Table 3 later.

[Evaluation of Adhesiveness]

Each cured film formation composition of an Example and a comparative example was apply | coated on the TAC film by 4 micrometers of Wet film thickness using the bar coater. Heat-drying was performed in a thermocyclic oven for 60 second at the temperature of 110 degreeC, respectively, Then, this coating film was exposed at 1000mJ / cm <^2>, and the cured film was formed on TAC film, respectively.

On this cured film, the polymer liquid crystal solution RMS03-015 made by Merck Co., Ltd. was apply | coated to Wet film thickness of 6 micrometers using the bar coater. The coating film on this board | substrate was exposed at 500mJ / cm <^2> , and the phase difference material was produced.

The retarder was cut with a cutter knife so as to be 5 x 5 spaces at 1 mm intervals. On this sheath, the cellophane tape peeling test was done using Scotch tape. Evaluation was made into what the thing which peeled off even if one of the space | columns which remain | survived without peeling all 25 space | columns. The evaluation results are summarized in Table 3 later.

As shown in Table 3, the orientation material obtained using the cured film formation composition of an Example showed the favorable vertical orientation similarly to the orientation material obtained using the cured film formation composition of a comparative example.

The cured film obtained using the cured film formation composition of an Example showed the outstanding adhesiveness. On the other hand, the cured film obtained using the cured film formation composition of a comparative example was difficult to acquire adhesiveness.

Industrial availability

The cured film formation composition which concerns on this invention is very useful as a material which forms the orientation material for forming the liquid crystal aligning film of a liquid crystal display element, or the optically anisotropic film provided in the inside or the exterior of a liquid crystal display element, Especially, IPS- It is suitable as an optical compensation film material of a circular polarizing plate used as an antireflection film of LCD and an organic EL display.

Claims (7)

(A) a polymer having a vertically oriented group and a polymerizable group containing a C = C double bond, and
(B) radical polymerization initiator
As a cured film formation composition containing
Said vertical orientation group is group represented by following formula (1), The cured film formation composition characterized by the above-mentioned.
[Formula 1]

(In formula [1],
Y ¹ represents a single bond or a bonding 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 hetero ring, Any hydrogen atom on the cyclic group is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom May be,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having a steroid skeleton as 17 to 30 carbon atoms, and optionally Hydrogen atom may be substituted with 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, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom Maybe,
Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on these cyclic groups is a hydroxy group, an alkyl group having 1 to 3 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms May be substituted with 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 the integer of 0-4, and when n is 2 or more, Y <^5> may be same or different,
Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms,
The 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 either linear, branched or cyclic. Or a combination thereof,
In addition, the alkylene group for Y ² and Y ³ , and the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxyl group for Y ⁶ are interrupted by a bond of 1 to 3 unless the bonding groups are adjacent to each other. Maybe
Furthermore, 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 _2-. Or when Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having the steroid skeleton, the -CH ₂ -CH (OH) —CH ₂ —, this alkylene group, this alkyl group and this fluorine-containing alkyl group may be bonded via a group and a bonding group adjacent to these,
And the linking group represents a group selected from the group consisting of -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O-, and -NH-CO-NH-. ,
Provided that each of Y ² to Y ⁶ represents a single bond, 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, -CH ₂ -CH (OH ) -CH ₂ -, the sum of carbon atoms of 1 to 18 alkyl group, a carbon atom number of 1 to 18 fluorinated alkyl group, a carbon atom number of 1 to 18 carbon atoms and an alkoxyl group of 1 to 18 carbon atoms, a fluorine-containing alkoxyl group of the 6 ~ 30). The method of claim 1,
In the polymer of (A) component, the cured film formation composition whose polymerizable group containing C = C double bond is at least 1 sort (s) chosen from the group which consists of an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group. . The method according to claim 1 or 2,
(C) Cured film formation composition which further contains at least 1 sort (s) chosen from the group which consists of a monomer and polymer which have a polymeric group containing C = C double bond. The method according to any one of claims 1 to 3,
Cured film formation composition containing 0.1 mass part-50 mass parts (B) component based on 100 mass parts of (A) component. The method according to claim 3 or 4,
Cured film formation composition containing 10 mass parts-1000 mass parts (C) component based on 100 mass parts of (A) component. It is obtained by hardening | curing the cured film formation composition of any one of Claims 1-5, The orientation material characterized by the above-mentioned. It is formed using the cured film obtained from the cured film formation composition of any one of Claims 1-5, The phase difference material characterized by the above-mentioned.