KR102662074B1 - Cured film forming 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.)[Problem] To provide an alignment material that has excellent vertical alignment and adhesion and can vertically align polymerizable liquid crystals with high sensitivity even on a resin film, and a cured film-forming composition for providing a phase difference material using this alignment material.
[Solution] A cured film-forming composition containing (A) a polymer having a polymerizable group containing a vertical alignment group and a C=C double bond, and (B) a radical polymerization initiator, wherein the vertical alignment group is represented by the following formula (1): A cured film forming composition, characterized in that the group is displayed.

(In formula [1], Y ¹ and Y ² represent a single bond, etc., 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, etc., Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, 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 with 1 to 18 carbon atoms, etc.)

Description

Cured film forming composition, orientation material and phase difference material

The present invention relates to a cured film forming composition suitable for a vertical alignment material that vertically aligns liquid crystal molecules. 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 liquid crystal having positive dielectric anisotropy (△ε>0). Related to cured film forming compositions, orientation materials, and retardation materials useful for producing +C plates (positive C plates) used to improve viewing angle characteristics or viewing angle characteristics of circular polarizers used as anti-reflection films in organic EL displays will be.

IPS-LCD is characterized by a small change in luminance/color depending on the viewing angle because the liquid crystal molecules do not tilt in the vertical direction. However, it is difficult to increase the contrast ratio, luminance, and response speed as a weakness. For example, as disclosed in Patent Document 1, in the IPS-LCD at the beginning of the proposal, a compensation film for the viewing angle is not used, and in an IPS-LCD that does not use a compensation film for the viewing angle, the dark state of the tilt angle is Due to relatively large light leakage, it has the disadvantage of showing a low contrast ratio value.

Patent Document 2 discloses an IPS-LCD compensation film using +C plate and +A plate (positive A plate). In this document, the following configuration is shown for the liquid crystal display device described here.

1) A liquid crystal layer with horizontal alignment is sandwiched between two substrates supplied by an electrode that can apply an electric field parallel to the liquid crystal layer surface.

2) One or more +A plates and +C plates are inserted into 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 +A plate and +C plate in the thickness direction of the protective film of the polarizer is not shown (TAC, COP, PNB).

In addition, the +A plate and +C plate are designed to provide an IPS-LCD with high contrast characteristics and low color shift at front and tilt angles by minimizing light leakage in the dark state at tilt angles. An IPS-LCD having been disclosed (Patent Document 3). Furthermore, a proposal has been made to use a +C plate to improve the viewing angle characteristics of a circularly polarizing plate used as an anti-reflection film for organic EL displays (Patent Document 5).

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

As previously proposed, the +C plate can compensate for light leakage in areas where the viewing angle of the polarizer is large, so it is very useful as an optical compensation film for circular polarizers used as anti-reflection films for IPS-LCDs and organic EL displays. do. However, it is difficult to achieve vertical alignment (positive C plate) using the conventionally known stretching treatment method.

In addition, conventionally proposed vertical alignment films using polyimide require the use of a solvent for polyimide such as N-methyl-2-pyrrolidone in film production. Therefore, this is not a problem for glass substrates, but when the substrate is a film, there is a problem that damage is caused to the substrate when forming an alignment film. In addition, vertical alignment films using polyimide require firing at high temperatures, and there is a problem that the film substrate cannot withstand high temperatures.

Furthermore, a method of forming a vertically aligned film has been proposed by directly treating the substrate with a silane coupling agent having a long-chain alkyl, etc.; however, in the case where hydroxyl groups do not exist on the surface of the substrate, treatment is difficult and the substrate is limited. (Patent Document 4).

Recently, in response to the demand for reducing manufacturing costs, there is a demand for so-called roll-to-roll production on low-cost resin films such as TAC (triacetylcellulose) film and COP (cycloolefin polymer) film. However, with alignment films formed from conventional materials as described above, it has been difficult to manufacture +C plates on resin films.

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

The present invention was made based on the above-mentioned knowledge and examination results, and the problem to be solved is to provide excellent vertical alignment, transparency and solvent resistance required for an optical compensation film, and further improve substrate and polymerizability. The object of the present invention is to provide a cured film forming composition for providing an alignment material that has adhesion to the liquid crystal layer and can stably orient polymeric liquid crystals vertically even on a resin film under low temperature and short firing conditions.

Another object of the present invention is to obtain from the cured film forming composition, which has excellent vertical alignment and adhesion, is solvent resistant, and stably produces polymerizable liquid crystals even on a resin film under low temperature and short time firing conditions. The object is to provide a phase difference material useful for a +C plate formed using an alignment material that can be vertically oriented and the alignment material.

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

In order to achieve the above object, the present inventors have carefully studied and selected a cured film forming material based on a polymer having a vertical alignment group and a polymerizable group containing a C=C double bond, thereby providing excellent vertical alignment and adhesion. By discovering that a cured film having a can be formed, the present invention was completed.

That is, the present invention, as a first aspect,

(A) A polymer having a vertical alignment group and a polymerizable group containing a C=C double bond, and

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

It relates to a cured film forming composition, wherein the vertical alignment group is a group represented by the following formula (1).

[Formula 1]

(In equation [1],

Y ¹ represents a single bond or linking group,

Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms, -CH ₂ -CH(OH)-CH ₂ -, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, 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. It 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 heterocycle, or a divalent organic group having 17 to 30 carbon atoms and a steroid skeleton, and any of the cyclic groups A hydrogen atom may be substituted with a hydroxyl group, an alkyl group with 1 to 3 carbon atoms, an alkoxyl group with 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, a fluorine-containing alkoxyl group with 1 to 3 carbon atoms, or a fluorine atom. You can,

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 with 1 to 3 carbon atoms, or an alkoxyl group with 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 an integer from 0 to 4, and when n is 2 or more, Y ⁵ may be the same or different,

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

The alkylene group for Y ² and Y ³ , the substituent on the cyclic group, and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group for Y ⁶ are either linear, branched, or cyclic. Or it may be a combination of these,

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 1 to 3 bonding groups unless the bonding groups are adjacent to each other. There may be,

Furthermore, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents -CH ₂ -CH(OH)-CH ₂ - Or, or when Y ² or Y ³ represents an alkylene group, or when Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, this divalent cyclic group, this divalent organic group having a steroid skeleton, or -CH ₂ -CH (OH)-CH ₂ -, this alkylene group, this alkyl group, and this fluorine-containing alkyl group may be bonded to a group adjacent to them through a bonding group,

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- ,

However, a single bond as represented by each of 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, -CH ₂ -CH(OH )-CH ₂ -, the total number of carbon atoms of an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group with 1 to 18 carbon atoms is 6. ~30).

As a second viewpoint, in the polymer of component (A), the polymerizable group containing a C=C double bond is at least one selected from the group consisting of an acrylic group, a methacryl group, a vinyl group, an allyl group, and a maleimide group. , relates to the cured film forming composition described in the first viewpoint.

As a third aspect, forming a cured film according to the first or second aspect, further comprising at least one selected from the group consisting of a monomer and a polymer having a polymerizable group containing a (C)C=C double bond. It relates to composition.

As a fourth viewpoint, it relates to the cured film forming composition according to any one of the first to third viewpoints, which contains 0.1 parts by mass to 50 parts by mass of component (B) based on 100 parts by mass of component (A). .

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

As a sixth viewpoint, it relates to an orientation material obtained by curing the cured film forming composition according to any one of the first to fifth viewpoints.

As a seventh viewpoint, it relates to a phase difference material formed using a cured film obtained from the cured film forming composition according to any one of the first to fifth viewpoints.

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

According to the second aspect of the present invention, it is possible to provide an alignment material that has excellent vertical alignment properties and can stably vertically align polymerizable liquid crystals under low temperature and short time firing conditions.

According to the third aspect of the present invention, it is possible to provide a retardation material that can be formed with high efficiency even on a resin film and has high transparency, high solvent resistance, and adhesion to the substrate and the liquid crystal film.

<Curated film forming composition>

The cured film forming composition of the present invention contains a polymer having a vertical alignment group as component (A) and a polymerizable group containing a C=C double bond, and a radical polymerization initiator as component (B). The cured film forming composition of the present invention is selected from the group consisting of monomers and polymers having a polymerizable group containing a C=C double bond as the component (C) in addition to the components (A) and (B). It may also contain at least one type. Additionally, other additives may be contained as long as they do not impair the effect of the present invention.

Hereinafter, details of each component will be described.

<(A) Ingredient>

Component (A) contained in the cured film forming composition of the present invention is a polymer having a polymerizable group containing a vertical alignment group and a C=C double bond.

In this specification, the vertically aligned group refers to a group containing a hydrocarbon group having about 6 to 30 carbon atoms, for example, and specifically refers to a group represented by the formula [1] described later.

Therefore, examples of the monomer having a vertically aligned group include monomers having a hydrocarbon group having about 6 to 30 carbon atoms. Examples of the hydrocarbon group having 6 to 30 carbon atoms include straight-chain, branched or cyclic alkyl groups with 6 to 30 carbon atoms or hydrocarbon groups with 6 to 30 carbon atoms containing an aromatic group. Therefore, specific examples of monomers containing a hydrocarbon group having 6 to 30 carbon atoms include alkyl esters of acrylic acid, alkyl esters of methacrylic acid, alkyl vinyl ethers, 2-alkyl styrene, 3-alkyl styrene, 4-alkyl styrene, N -Alkylmaleimides include those in which the alkyl group has 6 to 30 carbon atoms, or those in which the alkyl group of these monomers is substituted with a hydrocarbon group with 6 to 30 carbon atoms, including the aromatic group with 6 to 30 carbon atoms.

More specifically, the vertically aligned group is a group represented by the following formula [1].

[Formula 2]

In formula [1], Y ¹ represents a single bond or a linking group.

In formula [1], Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms, or -CH ₂ -CH(OH)-CH ₂ -.

Additionally, Y ² may include a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, and any hydrogen atom on these cyclic groups may be an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, or an alkyl group with 1 to 3 carbon atoms. It may be substituted with a real group, a fluorine-containing alkyl group with 1 to 3 carbon atoms, a fluorine-containing alkoxyl group with 1 to 3 carbon atoms, or a fluorine atom.

The heterocyclic rings 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 pyrimidine ring. Polyazine 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 Sol ring, acridine ring, etc. are mentioned, and more preferable ones include pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, These are 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, and the alkoxyl group includes an oxygen atom -O- in the group mentioned as a specific example of the alkyl group. A combined group can be mentioned. Additionally, examples of the fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group or alkoxyl group is replaced with a fluorine atom.

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 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, a hydroxy group, or the number of carbon atoms It may be substituted with an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom.

The alkyl group and the like mentioned as the heterocycle and substituent may be those mentioned in Y ² described above.

Furthermore, Y ⁴ may be a divalent organic group having 17 to 30 carbon atoms and a steroid skeleton. Preferred examples include cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estryl, 11α-hydroxymethylsteryl, 11α-progesteryl, and 2 hydrogen atoms from a structure selected from nosteryl, melatranil, methyltestosteryl, norethisteryl, pregnenonyl, β-sitosteryl, stigmasteryl, testosterone, and cholesterol acetate ester. It is a divalent group with a structure in which the dog has been removed. More specifically, for example, it is as follows.

[Formula 3]

(In the formula, * indicates the binding position.)

Among these, 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 17 to 30 carbon atoms and a steroid skeleton.

In 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, 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 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom. The alkyl group and the like mentioned as the heterocycle and 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.

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

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

Among these, Y ⁶ is preferably an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 10 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group with 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. Particularly preferably, Y ⁶ is an alkyl group having 1 to 16 carbon atoms or an alkoxyl group having 1 to 16 carbon atoms.

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 above formula [1] may be 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-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, etc. are mentioned.

Examples of the alkylene group include a divalent group obtained by removing one arbitrary hydrogen atom from the alkyl group.

The alkoxyl group includes a group in which an oxygen atom -O- is bonded to the group mentioned as a specific example of the alkyl group.

Additionally, examples of the fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group or alkoxyl group is replaced with a fluorine atom.

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

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 1 to 3 bonding groups unless the bonding groups are adjacent to each other. It may be.

Furthermore, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents -CH ₂ -CH(OH)-CH ₂ - or when Y ² or Y ³ represents an alkylene group, or when Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, this divalent cyclic group, this divalent organic group having a steroid skeleton, or -CH ₂ - CH(OH)-CH ₂ -, this alkylene group, this alkyl group, and this fluorine-containing alkyl group may be bonded to a group adjacent to them through a bonding group.

In addition, the linking 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, a single bond as 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, -CH ₂ -CH(OH )-CH ₂ -, the total number of carbon atoms of an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group with 1 to 18 carbon atoms is 6. ~30, for example 6~20.

Among these, when considering the vertical alignment 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, especially 8 to 16 carbon atoms.

In the polymer of component (A), polymerizable groups containing a C=C double bond include acrylic groups, methacryl groups, vinyl groups, allyl groups, and maleimide groups.

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

In the polymer of component (A), the specific side chain having a polymerizable group containing the C=C double bond preferably has 3 to 16 carbon atoms and has an unsaturated bond at the terminal, and is represented by formula (b2) Particularly preferred are the specific side chains represented by .

[Formula 4]

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 plurality of organic groups selected from this group. It is a divalent organic group made up of a combination of divalent organic groups. R ⁵¹ may contain an ester bond, an ether bond, an amide bond, -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 a specific side chain in which R ⁵² is a hydrogen atom is preferable, and more preferably, it is a specific side chain in which the terminal is an acryloyl group, methacryloyl group, or styryl group. .

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

Another method is to react a polymer having a specific functional group with a compound having a group that reacts with a specific functional group and a vertically oriented group, or a compound having a group that reacts with a specific functional group and a polymerizable group containing a C=C double bond. , the polymer of component (A) can be obtained.

Here, the specific functional group refers to functional groups such as carboxyl group, epoxy group, hydroxy group, amino group with active hydrogen, phenolic hydroxy group, or isocyanate group, or multiple types of functional groups selected from these.

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

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

Below, specific examples of the monomer required to obtain the polymer having the above specific functional group, that is, the specific monomer, are given. However, it is not limited to these.

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

Monomers having an epoxy group include, for example, glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, allyl glycidyl ether, and 3-ethenyl-7-oxa. Bicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide may be mentioned.

Monomers having a hydroxy group include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 4-hydroxy 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, etc. You can.

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

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

Examples of monomers having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, and m-tetramethylxyleneisocyanate.

Additionally, in the present invention, when obtaining a polymer having a specific functional group, in addition to the specific monomer, a monomer that is copolymerizable with this monomer but does not have a specific functional group can be used together.

Specific examples of such monomers include acrylic acid ester compounds or methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds, which have a structure different from that of the specific monomer. You can.

Hereinafter, specific examples of the monomers will be given, but they are not limited to these.

Acrylic acid ester compounds having a structure different from the above specific monomer include, 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 Latex, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutylacrylate, 2-methyl-2-adamantyl Acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Methacrylic acid ester compounds having a structure different from the above specific monomer include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and 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.

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

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

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

In addition, the polymer having the above-mentioned specific functional group can be suitably used as a commercial product.

Specific examples of commercially available polymers having one or more epoxy groups in the side chain or terminal include bisphenol A type epoxy resins such as jER1001, 1002, 1003, 1004, 1055, 1007, 1009, Copper 1010, Copper 834, Copper 828 (above, manufactured by Mitsubishi Chemical Corporation), etc., and bisphenol F type epoxy resins include jER806, Copper 807 (above, manufactured by Mitsubishi Chemical Corporation), etc., and phenol novolak type. The epoxy resins include jER152, 154 (manufactured by Mitsubishi Chemical Corporation), EPPN201, 202 (manufactured by Nippon Explosives Co., Ltd.), etc., and the cresol novolak-type epoxy resin is ECN-1299 (manufactured by Mitsubishi Chemical Corporation). Asahi Chemical Co., Ltd.), EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Explosives Co., Ltd.), jER80S75 (manufactured by Mitsubishi Chemical Co., Ltd.) ), etc., as the bisphenol A novolac type epoxy resin, jER157S70 (manufactured by Mitsubishi Chemical Corporation), etc., and as the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of polyol, EHPE- 3150 (manufactured by Daicel Co., Ltd.), etc. can be mentioned.

Specific examples of commercially available polymers having one or more hydroxy groups in the side chain or terminal, and specific examples of polyether polyols include Adeka Polyether P series, G series, EDP series, BPX series, FC series, and CM manufactured by ADEKA. Series, Nichiyu Uniox (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG- Specific examples of polyester polyol include 3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, Nonion (registered trademark) LT-221, ST-221, OT-221, etc. DIC 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, Kura Raye 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., Polycapro Specific examples of lactone polyols include Polylite (registered trademark) OD-X-2155, OD-X-640, and OD-X-2568 manufactured by DIC, Placel (registered trademark) 205, L205AL, and 205U manufactured by Daicel Chemicals. Examples include 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc.

The polymer of component (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 150,000, and still more preferably 3,000 to 100,000. If the weight average molecular weight is excessive (exceeding 200,000), solubility in solvents may decrease and handling properties may deteriorate. If the weight average molecular weight is too low (less than 1,000), curing may be insufficient during photocuring, resulting in poor solvent resistance and poor handling properties. Heat resistance may deteriorate.

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

In the polymer of component (A), the presence ratio of the vertically aligned group is preferably 3 mol% to 50 mol%, and more preferably 5 mol% to 45 mol%, per 100 moles of total repeating units of the polymer. If it is less than 3 mol%, vertical alignment may become insufficient, and if it is more than 50 mol%, it may adversely affect adhesion to the liquid crystal.

In the polymer of component (A), the presence ratio of a polymerizable group containing a C=C double bond is preferably 20 mol% to 97 mol%, and 25 mol% to 95 mol%, per 100 moles of total repeating units of the polymer. % is more preferable. If it is less than 20 mol%, curing may become insufficient, and if it is more than 97 mol%, vertical alignment may become insufficient.

<(B) Ingredient>

Component (B) in the cured film forming composition of the present invention is a radical polymerization initiator.

As the radical polymerization initiator, it is possible to use known ones, for example, alkylphenones, benzophenones, acylphosphine oxides, Michler's benzoylbenzoates, oxime esters, tetramethylthiuram mono. Sulfides, thioxanthone, etc. can be mentioned.

Examples of the radical polymerization initiator used in the present invention include α-diketones such as diacetyl; acylophosphones such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Thioxanthone, 2,4-diethylthioxanthone, 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, tribromomethylphenylsulfone, and tris(trichloromethyl)-s-triazine; [1,2'-bisimidazole]-3,3',4,4'-tetraphenyl, [1,2'-bisimidazole]-1,2'-dichlorophenyl-3,3',4, bisimidazoles such as 4'-tetraphenyl, peroxides such as di-tert-butyl peroxide; and acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Commercially available products include Igacure 184, 369, 379EG, 651, 500, 907, CGI369, CG24-61, OXE02, Lucirin LR8728, Lucirin TPO, Darocure 1116, 1173 (above, BASF Co., Ltd.), Yube. Examples include those sold commercially under brand names such as Creel P36 (manufactured by UCB Co., Ltd.).

Among the above, 1-[2-methyl-4-methylthiophenyl]-2-morpholino-1-propanone, 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' -Combined use of bisimidazoles, 4,4'-bis(diethylamino)benzophenone, and mercaptobenzothiazole, Lucirin TPO (brand name), Igacure 651 (brand name), Igacure 369 (brand name), Igacure 907 (brand name) and Igacure OXE02 (brand name) are preferred.

The radical polymerization initiator may be used individually or in combination of two or more types.

The radical polymerization initiator can be used in an amount of 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, based on 100 parts by mass of component (A). If the amount of radical polymerization initiator used is less than the above range, it is likely to be affected by deactivation of radicals by oxygen (reduction in sensitivity), and if it is more than the above range, compatibility tends to worsen or storage stability decreases.

<(C) Ingredient>

The cured film forming composition of the present invention may contain, as the (C) component, at least one type selected from the group consisting of monomers and polymers having a polymerizable group containing a C=C double bond.

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

Hereinafter, the monomers and polymers having a polymerizable group containing a C=C double bond as the (C) component of the present invention include two polymerizable groups containing a C=C double bond per molecule from the viewpoint of increasing film strength. Monomers and polymers having the above are preferred. Below, an example of a suitable compound is given, but component (C) is not limited to these examples.

Compounds having two (meth)acryloyl groups include, 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 glycol di(meth)acrylate (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1 , 10-decanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ] decanedimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate , 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, trishydroxyethyl isocyanurate di. (meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, undecyleneoxyethylene glycol di(meth)acrylate, 1,3-adamane Thanediol di(meth)acrylate, 1,3-adamantane dimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, etc. are mentioned.

Compounds having two or more (meth)acryloyl groups can suitably use commercial products, for example, light acrylate 3EG-A, light acrylate 4EG-A, light acrylate 9EG-A, light acrylate. 14EG-A, light acrylate PTMGA-250, light acrylate NP-A, light acrylate MPD-A, light acrylate 1.6HX-A, light acrylate 1.9ND-A, light acrylate MOD-A, light acrylic Late DCP-A, Light Acrylate BP-4EAL, Light Acrylate BP-4PA, Light Acrylate HPP-A, Light Ester G-201P, Light Ester P-2M, Light Ester EG, Light Ester 2EG, Light Ester 3EG, Light ester 4EG, Light ester 9EG, Light ester 14EG, Light ester 1.4BG, Light ester NP, Light ester 1.6HX, Light ester 1.9ND, Light ester G-101P, Light ester G-201P, Light ester BP-2EMK [above , all manufactured by Kyoeisha 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, East A-BPE-4, East A-BPEF, East A-BPP-3, East A-DCP, East A-DOD-N, East A-HD-N, East A-NOD-N, Dong APG-100, Dong APG-200, Dong APG-400, Dong APG-700, Dong A-PTMG-65, Dong 1G, Dong 2G, Dong 3G, Dong 4G, Dong 9G, Dong 14G, Dong 23G, Dong 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, 701, 9PG [all manufactured by Shinnakamura 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 manufactured by Hitachi Chemical Co., Ltd.] ; DPGDA, HODA, TPGDA, EBECRYL (registered trademark) 145, 150, IRR214-K, PEG400DA-D, EBECRYL (registered trademark) 11, HPDNA (manufactured by Daicell Allnex Co., Ltd.); Biscote #195, Copper #230, Copper #260, Copper #310HP, Copper #335HP, Copper #700HV, Copper #540, Copper #802, Copper #295 [all of the above, manufactured by Japan Synthetic Chemicals Co., Ltd.], etc. can be mentioned.

Compounds (trifunctional compounds) having three (meth)acryloyl groups include, for example, ethylene oxide-modified 1,1,1-trimethylolethane tri(meth)acrylate [ethylene oxide added mole number 3 to 30], Ethylene oxide-modified trimethylolpropane tri(meth)acrylate [ethylene oxide added moles 3-30], propylene oxide-modified trimethylolpropane tri(meth)acrylate [propylene oxide added moles 3-30], ethylene oxide-modified glycerin tri( Meth)acrylate [ethylene oxide added mole number 3-30], propylene oxide modified glycerin tri(meth)acrylate [propylene oxide added mole number 3-30], tris(2-(acryloyloxy)ethyl)isocyanurate , ε-caprolactone modified tris(2-(acryloyloxy)ethyl)isocyanurate [ε-caprolactone added mole number 1-30], 1,1,1-trimethylolethane tri(meth)acrylate, Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin tri(meth)acrylate, etc. are mentioned.

As the above-mentioned trifunctional compound, commercial products can be suitably used, for example, Viscot #360 (manufactured by Osaka Organic Chemicals Co., Ltd.); NK ester A-GLY-9E, A-GLY-20E, AT-20E (all manufactured by Shin Nakamura Chemical Co., Ltd.); TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [all manufactured by Daicell Allnex Co., Ltd.], Viscot #295, #300 [all manufactured by Osaka Organic Chemicals Co., Ltd.]; Light acrylate TMP-A, copper PE-3A, light ester TMP (all manufactured by Kyoeisha Chemical Co., Ltd.); NK Ester A-9300, A-9300-1CL, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT [all Shinnakamura Chemicals Made by Industrial Co., Ltd.]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [above, all manufactured by Daicell Allnex Co., Ltd.], etc. can be mentioned.

Compounds (tetrafunctional compounds) having four (meth)acryloyl groups include, for example, ethylene oxide-modified ditrimethylolpropane tetra(meth)acrylate [ethylene oxide added mole number 4 to 40], ethylene oxide-modified pentaerythritol. Tetra(meth)acrylate [ethylene oxide added mole number 4-40], ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. are mentioned.

As the tetrafunctional compound, commercial products can be suitably used, for example, NK ester ATM-4E, copper ATM-35E (all manufactured by Shin Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) 40 (manufactured by Daicell Allnex Co., Ltd.), etc., Biscote #300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.); NK ester AD-TMP, copper A-TMMT (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.); Examples include EBECRYL (registered trademark) 140, 1142, and 180 (all manufactured by Daicell Allnex Co., Ltd.).

Compounds having five or more (meth)acryloyl groups (five or more functional compounds) include, for example, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate [ethylene oxide added mole number 6-60], ethylene oxide-modified tri. Pentaerythritol octa(meth)acrylate [ethylene oxide added mole number 6-60], dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, etc. You can.

As the above-mentioned compounds with five or more functional groups, commercial products can be suitably used, for example, NK Ester A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Viscot #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) ; Light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.); NK ester A-9550, A-DPH [above, all manufactured by Shin Nakamura Chemical Industry Co., Ltd.]; DPHA (manufactured by Daicel Allnex Co., Ltd.), etc. can be mentioned.

Bifunctional urethane (meth)acrylates include, for example, the (meth)acrylic acid adduct of phenylglycidyl ether, the urethanide of hexamethylene diisocyanate, and the (meth)acrylic acid adduct of phenylglycidyl ether. and urethanide with toluene diisocyanate.

As the above-mentioned difunctional urethane (meth)acrylate, commercial products can be suitably used, for example, AH-600, AT-600 (all manufactured by Kyoeisha Chemical Co., Ltd.); NK oligo U-2PPA, U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-W2A [All above, Shin Nakamura Chemical Co., Ltd. )my]; EBECRYL (registered trademark) 210, 215, 230, 244, 245, 270, 280/15IB, 284, 285, 4858, 8307, 8402, 8411, 8804, 8807 , No. 9227EA, No. 9270, KRM (registered trademark) 7735 [all manufactured by Daicell Allnex Co., Ltd.]; Shikou (registered trademark) UV-6630B, 7000B, 7461TE, 2000B, 2750B, 3000, 3200B, 3210EA, 3300B, 3310B, 3500BA, 3520TL, 3700B, 6640B [or more] , all manufactured by Japan Synthetic Chemicals Co., Ltd.], etc.

Specific examples of commercially available polyfunctional urethane (meth)acrylate compounds having three (meth)acryloyl groups include NK Oligo UA-7100 (manufactured by Shin Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) 204, 205, 264, 265, 294/25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, 8667 [or more] , all manufactured by Daicell Allnex Co., Ltd.]; Shikou (registered trademark) UV-7550B, 7000B, 7510B, 7461TE, 2750B (all manufactured by Japan Synthetic Chemicals Co., Ltd.), etc.

Specific examples of commercially available polyfunctional urethane (meth)acrylate compounds having four (meth)acryloyl groups include EBECRYL (registered trademark) 8210, EBECRYL (registered trademark) 8405, and KRM (registered trademark) 8528 [all of which are Daicell Allnex]. (subject]; Shikou (registered trademark) UV-7650B (manufactured by Japan Synthetic Chemicals Co., Ltd.), etc. can be mentioned.

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

As the above-mentioned urethane (meth)acrylate having more than 5 functions, commercially available products can be suitably used, for example, UA-306H, UA-306T, UA-306I, UA-510H [all of the above 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 Co., Ltd.); EBECRYL (registered trademark) 220, 1290, 5129, 8254, 8301R, KRM (registered trademark) 8200, 8200AE, 8904, 8452 [all manufactured by Daicell Allnex Co., Ltd.]; Shikou (registered trademark) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B [all manufactured by Nippon Synthetic Chemicals Co., Ltd.]. there is.

Component (C) of the present invention may be a polymer compound having at least one side chain in the molecule whose terminal is a polymerizable unsaturated bond. Examples of such a polymer compound having a side chain whose terminal is a polymerizable unsaturated bond include preferably a polymer compound having a (meth)acryloyl group in two or more side chains within the molecule.

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

The weight average molecular weight of the polymer compound of component (C) is preferably 1,000 to 200,000, and 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 exhibited. On the other hand, if the molecular weight is excessive and exceeds 100,000, it may not be dissolved in the composition.

Compounds that are these (C) components include, for example, Acryte 8BR-930M, 8UH-1006, 8KQ-2001, 8KX-078, and 1SX-1055 (manufactured by Daisei Fine Chemical Co., Ltd.), Polymers such as SMP-250A, SMP-360A, and SMP-550A (above, manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned.

The content when containing component (C) 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 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 this time can dissolve component (A), component (B), and, if necessary, component (C) and/or other additives described later, and its type and structure are not particularly limited.

Specific examples of solvents include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, and 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. ester, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy -3-Methyl butanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxymethyl propionate, ethyl 3-ethoxypropionate, 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.

When producing an orientation material by forming a cured film on a resin film using the cured film forming composition of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2 -Heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. are preferred because they are solvents to which the resin film is resistant.

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

<Other additives>

Furthermore, the cured film forming composition of the present invention may contain a sensitizer, adhesion improver, silane coupling agent, surfactant, rheology modifier, pigment, dye, storage stabilizer, and anti-foaming agent as necessary, as long as the effect of the present invention is not impaired. , antioxidants, etc.

<Preparation of cured film forming composition>

The cured film-forming composition of the present invention contains a polymer having a polymerizable group containing a vertical alignment group and a C=C double bond as component (A), a polymerization initiator as component (B), and, if necessary, the polymerization initiator as component (C). It is a composition that may contain at least one type selected from the group consisting of monomers and polymers having a polymerizable group containing a C=C double bond, and other additives as long as they do not impair the effect of the present invention. And usually, they are used in the form of a solution 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 component (B) based on 100 parts by mass of component (A) and component (A).

[2]: 0.1 parts by mass to 50 parts by mass based on 100 parts by mass of component (A), component (A), 10 parts by mass to 1000 parts by mass based on 100 parts by mass of component (B), component (A). (C) A cured film-forming composition containing a component and a solvent.

The mixing ratio, preparation method, etc. when using the cured film forming composition of the present invention as a solution are described in detail below.

The ratio of 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% by mass to 50% by mass. It is mass %, and more preferably, it is 2 mass % to 20 mass %. Here, solid content refers to what the solvent is removed from all components of the cured film forming composition.

The preparation method of the cured film forming composition of the present invention is not particularly limited. The preparation method includes, for example, mixing the solution of component (A) dissolved in a solvent with component (B) and further component (C) at a predetermined ratio to obtain a uniform solution, or this preparation method. In an appropriate step, other additives may be added and mixed as needed.

In addition, it is preferable to use the solution of the prepared cured film-forming composition after filtering it using a filter with a pore diameter of about 0.2 μm, etc.

<Curated film, orientation material, and phase difference material>

A solution of the cured film forming composition of the present invention is applied to a substrate (e.g., a silicon/silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate). , ITO substrate, etc.) or film substrate (e.g., triacetylcellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) ) Film, acrylic film, polyethylene film, etc., form a coating film by applying bar coat, rotational application, drip application, roll application, slit application, rotational application after slit, inkjet application, printing, etc. , After that, a cured film can be formed by heating and drying in a hot plate or oven, etc. This cured film can be applied as is as an orientation material.

Conditions for heat drying include that the crosslinking reaction using the crosslinking agent proceeds to the extent that the components of the cured film (alignment material) do not dissolve in the polymerizable liquid crystal solution applied thereon, for example, at a temperature of 60°C to 200°C. A heating temperature and heating time appropriately selected from the range of °C and a time range of 0.4 minutes to 60 minutes are adopted. The heating temperature and heating time are preferably 70°C to 160°C and 0.5 to 10 minutes.

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

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 alignment can be applied onto this alignment material and aligned on the alignment material. Then, by curing the aligned phase difference material as is, a phase difference material can be formed as a layer having optical anisotropy. And, when the substrate forming the orientation material is a film, it is useful as a retardation film.

Additionally, using two substrates formed as described above and having the alignment material of the present invention, the alignment materials on both substrates are placed to face each other with a spacer interposed therebetween, and then liquid crystal is injected between these substrates, so that the liquid crystal It can also be used as an oriented liquid crystal display device.

In this way, the cured film-forming composition of the present invention can be suitably used in the manufacture of various retardation materials (retardation films), liquid crystal display elements, etc.

Example

Hereinafter, the present invention will be described in detail with reference to examples of the present invention, but the present invention is not to be construed as limited to these.

[Abbreviated symbols used in examples]

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

<Ingredient A>

LAA: Lauryl acrylate

PAA: palmityl acrylate

HEMA: 2-hydroxyethyl methacrylate

GMA: Glycidyl methacrylate

AOI: Karens AOI made by Showa Denko Co., Ltd.

AIBN: α,α’-azobisisobutyronitrile

LA: Lauric acid

M100: 3,4-epoxycyclohexylmethyl methacrylate

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

<Ingredient B>

IRG: IRGACURE 907 made by BASF

OXE: IRGACURE OXE 02 made by BASF

<Component C>

DPHA: Dipentaerythritol hexaacrylate manufactured by Dicell Allnex Co., Ltd.

SMP: UV-curable acrylic polymer SMP-550A manufactured by Kyoeisha Chemical Co., Ltd.

<Other>

MAA: methacrylic acid

CYM303: Hexamethoxymethylmelamine

PTSA: p-toluenesulfonic acid monohydrate

<Solvent>

Each cured film forming composition of the 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 was determined as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd. It was measured.

Meanwhile, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in polystyrene conversion values.

Column temperature: 50℃

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

Flow rate: 1.0mL/min

Standard samples for creating a calibration curve: TSK standard polyethylene oxide (molecular weight approximately 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight approximately 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

<Polymerization Example 1>

3.0 g of LAA, 12.0 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution. The obtained acrylic copolymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic copolymer (P1). The Mn of the obtained acrylic copolymer was 14,000 and Mw was 38,000.

<Polymerization Example 2>

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

<Polymerization Example 3>

3.0 g of LAA, 12.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution. The obtained acrylic copolymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic copolymer (P3). The Mn of the obtained acrylic copolymer was 8,600 and Mw was 20,000.

<Polymerization Example 4>

1.5 g of LAA, 13.5 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 45.7 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution. The obtained acrylic copolymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic copolymer (P4). The Mn of the obtained acrylic copolymer was 15,000 and Mw was 32,000.

<Polymerization Example 5>

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

<Polymerization Example 6>

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

<Polymerization Example 7>

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 were dissolved in 107.0 g of PM and reacted at 80°C for 16 hours to obtain an acrylic copolymer solution (solid concentration: 25% by mass) (P7). The 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 as a reaction catalyst were dissolved in 30 g of PM and reacted at 110°C for 20 hours. . This solution was slowly 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 H-NMR analysis was performed 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 as a reaction catalyst were dissolved in 30 g of PM and reacted at 110°C for 20 hours. . This solution was slowly 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. ^1H -NMR analysis was performed to confirm 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 as a reaction catalyst were dissolved in 60 g of tetrahydrofuran. and reacted at 60°C for 5 hours. This solution was slowly 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 H-NMR analysis was performed to confirm 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 as a reaction catalyst were dissolved in 30 g of PM and reacted at 110°C for 20 hours. . This solution was slowly 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 H-NMR analysis was performed 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 as a reaction catalyst were dissolved in 30 g of PM and reacted at 110°C for 20 hours. . This solution was slowly 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. ^1H -NMR analysis was performed 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 and heated at 110°C. The reaction was performed for 20 hours. This solution was slowly 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 H-NMR analysis was performed 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 and incubated at 110°C. The reaction was performed for 20 hours. This solution was slowly 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 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 and heated at 110°C. The reaction was performed for 20 hours. This solution was slowly 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 H-NMR analysis was performed to confirm that the acrylic copolymer (PA-8) had an acroyl group.

<Example>

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

[Table 1]

<Comparative example>

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

[Evaluation of vertical orientation]

Each cured film-forming composition of the examples was applied to a wet film thickness of 4 μm on a TAC film using a bar coater. Each was heated and dried in a thermal circulation oven at a temperature of 110°C for 60 seconds, and then the coating film was exposed to 1000 mJ/cm ² to form a cured film on the TAC film.

On this cured film, polymerizable liquid crystal solution for vertical alignment RMS03-015 manufactured by Merck Co., Ltd. was applied to a wet film thickness of 6 μm using a bar coater. This coating film was exposed to light at 500 mJ/cm ² to produce a phase difference material.

For these manufactured phase difference materials, the incident angle dependence of the in-plane phase difference was measured using a phase difference measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. It was judged that vertical alignment occurred when the in-plane phase difference value at an incident angle of 0 degrees was 0 and the in-plane phase difference at an incident angle of ±50 degrees was in the range of 38±5 nm. The evaluation results are summarized in Table 3 below.

Each cured film forming composition of the comparative example was applied to a wet film thickness of 4 μm on the TAC film using a bar coater. Each was heated and dried in a thermal circulation oven at a temperature of 110°C for 60 seconds to form a cured film on the TAC film.

On this cured film, polymerizable liquid crystal solution for vertical alignment RMS03-015 manufactured by Merck Co., Ltd. was applied to a wet film thickness of 6 μm using a bar coater. This coating film was exposed to light at 500 mJ/cm ² to produce a phase difference material.

For these manufactured phase difference materials, the incident angle dependence of the in-plane phase difference was measured using a phase difference measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. It was judged that vertical alignment occurred when the in-plane phase difference value at an incident angle of 0 degrees was 0 and the in-plane phase difference at an incident angle of ±50 degrees was in the range of 38±5 nm. The evaluation results are summarized in Table 3 below.

[Evaluation of adhesion]

Each cured film-forming composition of Examples and Comparative Examples was applied to a TAC film with a wet film thickness of 4 μm using a bar coater. Each was heated and dried in a thermal circulation oven at a temperature of 110°C for 60 seconds, and then the coating film was exposed to 1000 mJ/cm ² to form a cured film on the TAC film.

On this cured film, polymerizable liquid crystal solution for vertical alignment RMS03-015 manufactured by Merck Co., Ltd. was applied to a wet film thickness of 6 μm using a bar coater. The coating film on this substrate was exposed to light at 500 mJ/cm ² to produce a phase difference material.

Cuts were made on this phase difference material with a cutter knife to form 5 × 5 cells at 1 mm width and length intervals. A cellophane tape peel test was performed using Scotch tape on this sheath. In the evaluation, those in which all 25 cells remained without peeling were rated as ○, and those in which even one cell was peeled were rated as ×. The evaluation results are summarized in Table 3 below.

As shown in Table 3, the orientation material obtained using the cured film-forming composition of the Example showed good vertical alignment, similarly to the orientation material obtained using the cured film-forming composition of the comparative example.

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

Industrial applicability

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 device or an optically anisotropic film provided inside or outside the liquid crystal display device, especially IPS- It is suitable as a material for the optical compensation film of circularly polarizing plates used as anti-reflection films in LCDs and organic EL displays.

Claims (7)

(A) A polymer having a vertical alignment group and a polymerizable group containing a C=C double bond, and
(B) Radical polymerization initiator
A vertical alignment material obtained by curing a cured film-forming composition containing,
A vertical alignment material, characterized in that the vertical alignment group is a group represented by the following formula (1).

(In equation [1],
Y ¹ represents a single bond or linking group,
Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms, -CH ₂ -CH(OH)-CH ₂ -, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, 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. It may be,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents 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 a steroid skeleton, and any hydrogen atom on the cyclic group is a hydroxy group, It may be 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,
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 with 1 to 3 carbon atoms, or an alkoxyl group with 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 an integer from 0 to 4, and when n is 2 or more, Y ⁵ may be the same or different,
Y ⁶ represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group with 1 to 18 carbon atoms,
The alkylene group for Y ² and Y ³ , the substituent on the cyclic group, and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group for Y ⁶ are either linear, branched, or cyclic. Or it may be a combination of these,
In addition, the alkylene group in Y ² and Y ³ and the alkyl group, fluorine-containing alkyl group, alkoxyl group, and fluorine-containing alkoxyl group in Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. There may be,
Furthermore, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² represents -CH ₂ -CH(OH)-CH ₂ - Or, or when Y ² or Y ³ represents an alkylene group, or when Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, this divalent cyclic group, this divalent organic group having a steroid skeleton, or -CH ₂ -CH (OH)-CH ₂ -, this alkylene group, this alkyl group, and this fluorine-containing alkyl group may be bonded to a group adjacent to them through a bonding group,
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- ,
However, a single bond as represented by each of 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, -CH ₂ -CH(OH )-CH ₂ -, the total number of carbon atoms of an alkyl group with 1 to 18 carbon atoms, a fluorine-containing alkyl group with 1 to 18 carbon atoms, an alkoxyl group with 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group with 1 to 18 carbon atoms is 6. ~30). According to paragraph 1,
In the polymer of component (A), the polymerizable group containing a C=C double bond is at least one selected from the group consisting of an acrylic group, a methacrylic group, a vinyl group, an allyl group, and a maleimide group. According to paragraph 1,
(C) A vertical alignment material further containing at least one member selected from the group consisting of monomers and polymers having a polymerizable group containing a C=C double bond. According to paragraph 1,
A vertical alignment material containing 0.1 parts by mass to 50 parts by mass of (B) component based on 100 parts by mass of (A) component. According to paragraph 3,
A vertical alignment material containing 10 to 1000 parts by mass of component (C) based on 100 parts by mass of component (A). delete A phase difference material formed using the vertical alignment material according to any one of claims 1 to 5.