KR102246723B1 - Cured film-forming composition, alignment material, and phase difference material - Google Patents

Abstract

[Task] To provide a cured film forming composition for providing an alignment material capable of vertically aligning a polymerizable liquid crystal with excellent vertical alignment and high sensitivity even on a resin film, and a retardation material using the alignment material.
[Solution] (A) a polymer having a vertical orientation group and a thermally crosslinkable functional group, and (B) a cured film forming composition comprising a crosslinking agent, an orientation material obtained by using the composition, and the composition Phase difference material, characterized in that obtained by using.

Description

Cured film forming composition, orientation material, and retardation material {CURED FILM-FORMING COMPOSITION, ALIGNMENT MATERIAL, AND PHASE DIFFERENCE MATERIAL}

The present invention relates to a composition for forming a cured film suitable for a vertical alignment material for vertically aligning liquid crystal molecules. In particular, the present invention is a liquid crystal display (LCD), specifically an IPS liquid crystal display (In-plane Switching LCD) filled with a liquid crystal (Δε>0) having positive dielectric anisotropy. It relates to a cured film forming composition, an alignment material, and a retardation material useful for preparing a +C plate (positive C plate), which is used to improve the viewing angle characteristic of an orientation switching LCD).

IPS-LCD is characterized by a small change in luminance/color change according to the viewing angle, since the inclination of the liquid crystal molecules in the vertical direction does not occur, and the difficulty of increasing the contrast ratio, luminance, and response speed can be cited as a weakness. For example, as disclosed in Patent Document 1, in the early IPS-LCD of the proposal, a compensation film of a viewing angle is not used, and in an IPS-LCD that does not use a compensation film of such a viewing angle, the inclination angle is in the dark state. There is a disadvantage in that the value of the contrast ratio is low due to the relatively large light leakage.

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

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

2) More than one +A plate and +C plate are sandwiched between two 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 so as to satisfy the following equation.

R _LC :R _+C :R _+A ≒1:0.5:0.25

5) The relationship between the retardation value of the +A plate and the +C plate in the thickness direction of the protective film of the polarizing plate is not disclosed (TAC, COP, PNB).

In addition, the +A plate and +C plate aimed at providing an IPS-LCD with 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. The having IPS-LCD is disclosed (Patent Document 3).

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

As previously proposed, the +C plate is very useful as an optical compensation film of an IPS-LCD because it can compensate for light leakage at a point where the viewing angle of the polarizing plate is large. However, it is difficult to develop vertical orientation (positive C plate) property in the conventionally known method by the stretching treatment.

In addition, for the conventionally proposed vertical alignment film using polyimide, it is necessary to use a polyimide solvent such as N-methyl-2-pyrrolidone for film formation. Accordingly, it is not a problem in the glass substrate, but when the substrate is a film, there is a problem that damage is given to the substrate when forming the alignment layer. In addition, in the vertical alignment film using polyimide, firing at high temperature is required, and there is a problem that the film base material cannot withstand high temperature.

In addition, a method of forming a vertical alignment film by directly treating the substrate with a silane coupling agent having a long chain alkyl, etc., has also been proposed, but there is a problem that the treatment is difficult and the substrate is limited when there is no hydroxy group on the surface of the substrate. (Patent Document 4).

The present invention has been made on the basis of the above findings and research results, and the problem to be solved is that it has excellent vertical orientation, and provides transparency and solvent resistance required for an optical compensation film. It is to provide a cured film forming composition for providing an alignment material capable of stably aligning the polymerizable liquid crystal vertically under firing conditions.

In addition, another object of the present invention is an alignment material that is obtained from the cured film forming composition, has excellent vertical alignment, and can stably vertically align a polymerizable liquid crystal even on a resin film under low-temperature and short-time firing conditions. It is to provide a retardation material useful for a +C plate formed using an alignment material.

In order to achieve the above object, the inventors of the present invention selected a cured film-forming material based on an acrylic copolymer having a long-chain alkyl group in the side chain as a result of intensive examination, thereby curing with excellent vertical orientation regardless of the type of substrate. It discovered that a film could be formed, and the present invention was completed.

That is, the present invention as a first aspect,

(A) a polymer having a vertical orientation group and a thermally crosslinkable functional group, and

(B) crosslinking agent

As a cured film forming composition containing,

The vertical orientation group relates to a cured film forming composition, characterized in that the group represented by the following formula (1).

[Formula 1]

(In Equation [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 heterocycle, and the above 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, a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle, or a divalent organic group having a steroid skeleton with 17 to 30 carbon atoms, and any hydrogen on the cyclic group It may be substituted with a valence, 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 an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, and the number of carbon atoms It may be substituted with a fluorine-containing alkyl group of 1 to 3, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom,

n represents an integer of 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 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 as Y 2} and Y ³ , and the substituent on the cyclic group or the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxy group as ^{Y 6 may be linear, branched, or cyclic, or a combination thereof.} There is,

Or the ^{alkylene group as Y 2} and Y ³ , and the alkyl group, ^{fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxy group as Y 6} may be interrupted by 1 to 3 linking groups as long as the linking groups are not adjacent,

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

And the bonding _{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, each of Y ¹ to Y ⁶ represents 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 having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms is 6 to 30).

As a 2nd viewpoint, it is related with the cured film formation composition as described in a 1st viewpoint in which the thermally crosslinkable functional group of (A) component is a hydroxy group, a carboxyl group, an amino group, or an alkoxysilyl group.

As a 3rd viewpoint, it is related with the cured film formation composition as described in a 1st viewpoint or a 2nd viewpoint, in which the crosslinking agent of (B) component is a crosslinking agent which has a methylol group or an alkoxymethyl group.

As a 4th viewpoint, it is related with the cured film formation composition in any one of 1st viewpoint to 3rd viewpoint containing (C) a crosslinking catalyst.

As a fifth viewpoint, it relates to the cured film formation composition according to any one of the first to fourth viewpoints containing 1 part by mass to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A). .

As a 6th viewpoint, it is related with the cured film formation composition as described in 4th viewpoint or 5th viewpoint containing 0.01 mass part-20 mass parts of (C) component based on 100 mass parts of (A) component.

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

As an eighth viewpoint, it relates to a retardation material characterized in that it is formed using a cured film obtained from the cured film forming composition according to any one of the first to sixth viewpoints.

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

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

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

<Cured film formation composition>

The cured film forming composition of the present invention contains a polymer having a vertical orientation group as a component (A) and a functional group capable of thermal crosslinking, and a crosslinking agent as a component (B). The cured film forming composition of the present invention may further contain a crosslinking catalyst as a component (C) in addition to the component (A) and the component (B). And, other additives may be contained as long as the effect of the present invention is not impaired.

Hereinafter, the details of each component will be described.

<(A) component>

The component (A) contained in the cured film forming composition of the present invention is a polymer having a vertical orientation group as a side chain and a thermally crosslinkable functional group (hereinafter, also referred to as a thermally crosslinkable group).

The polymer of the component (A) of the present invention is not particularly limited, but a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester, styrene, maleimide, etc. may be applied.

That is, the polymer of component (A) of the present invention may be, for example, an acrylic polymer (hereinafter also referred to as a specific copolymer) containing a functional group capable of thermal crosslinking with a vertical orientation group in the side chain, and the main chain of the polymer constituting the acrylic copolymer There is no particular limitation on the kind of the skeleton and other side chains.

The polymer of the component (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 150,000, and even more preferably 3,000 to 100,000. If the weight average molecular weight exceeds 200,000 and is excessive, the solubility in the solvent decreases and the handling property may decrease.If the weight average molecular weight is less than 1,000, the curing is insufficient during thermal curing, resulting in solvent resistance and Heat resistance may decrease.

(A) As a method for synthesizing the polymer of component, that is, an acrylic copolymer having a specific group such as a vertical alignment group in the side chain, a method of polymerizing a monomer having a vertical alignment group described later, or a method of polymerizing a monomer having a reactive group and vertical alignment property. It is easy to combine a compound having a group through a polymer reaction.

Among these, the polymer having a vertical orientation group and a thermal crosslinkable group as component (A) is a copolymer obtained by copolymerizing a monomer having a vertical orientation group and a monomer having a thermal crosslinkable group, that is, a copolymer having the vertical orientation group or a thermal crosslinkable group. It is easy to use a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as an acrylic acid ester, a methacrylic acid ester, styrene or maleimide.

In the present specification, the vertically oriented group refers to a group including a hydrocarbon group having 6 to 20 carbon atoms, for example, and specifically refers to a group represented by formula [1] described later.

Accordingly, as a monomer having a vertically oriented group, for example, a monomer having a hydrocarbon group having 6 to 20 carbon atoms can be mentioned. Examples of the hydrocarbon group having 6 to 20 carbon atoms include a linear, branched or cyclic hydrocarbon group having 6 to 20 carbon atoms including an alkyl group or an aromatic group having 6 to 20 carbon atoms. Therefore, specific examples of the monomer containing a hydrocarbon group having 6 to 20 carbon atoms include an alkyl ester of acrylic acid, an alkyl ester of methacrylic acid, an alkyl vinyl ether, 2-alkylstyrene, 3-alkylstyrene, 4-alkylstyrene, N -As the alkyl maleimide, the alkyl group having 6 to 20 carbon atoms is exemplified.

The vertical orientation group is more specifically, a group represented by the following formula [1], that is, the monomer having a vertical orientation group more specifically contains a group represented by the following formula [1], acrylic acid ester, methacrylic acid It is a monomer which has an unsaturated double bond, such as ester, styrene, and maleimide.

[Formula 2]

In formula [1], Y ¹ represents a single bond or a bonding 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 -.

Further, as Y ² , a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocycle can be mentioned, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxy having 1 to 3 carbon atoms. It may be substituted with an actual group, 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.

As the heterocycle, 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, pyri Dajin 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., and more preferable ones are 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, It is a pyrazolidine ring, a triazole ring, a pyrazine ring, and a benzimidazole ring.

Examples of the alkyl group used as the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group, and the alkoxyl group is a group in which an oxygen atom -O- is bonded to the group as a specific example of the alkyl group. Can be lifted. Further, examples of the fluorine-containing alkyl group and the fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group and the alkoxyl group is substituted with a fluorine atom.

^{Among these, it is preferable that Y 2} is a benzene ring or a cyclohexane ring from the viewpoint of ease of synthesis.

In the above formula [1], Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms.

In the formula [1], Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms. , It may be substituted with 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 heterocycle and the alkyl group used as a substituent may be ^{those of Y 2 described above.}

Further, as Y ⁴ , it may be a divalent organic group selected from organic groups having 17 to 30 carbon atoms and having a steroid skeleton. Preferred examples thereof are cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, elligosteryl, estril, 11α-hydroxymethylsteryl, 11α-progesteryl, and 2 hydrogen atoms from a structure selected from nosteryl, melatranil, methyl testosteryl, norethisteryl, pregnenonyl, β-sitosteryl, stigmasteryl, testosteryl, and cholesterol acetate It is a divalent group with a structure that has been removed. More specifically, it is as follows, for example.

[Formula 3]

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

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 an alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms. It may be substituted with an alkoxyl group of, 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 heterocycle and the alkyl group used as a substituent may be ^{those of Y 4 described above.}

Among these, ^{it is preferable that Y 5} is a benzene ring or a cyclohexane ring.

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

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

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 a C1-C12 alkyl group or a C1-C12 alkoxyl group. Particularly preferably, Y ⁶ is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

In addition, 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 or fluorine-containing alkoxy group in the definition in the above formula [1] may be linear, branched, or cyclic, or a combination thereof.

For example, 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-undee Real group, n-dodecyl group, n-tridecyl group, n-tetradecyl group and n-pentadecyl group.

Examples of the alkylene group include a divalent group in which one arbitrary hydrogen atom has been removed from the alkyl group.

Examples of the alkoxyl group include a group in which an oxygen atom -O- is bonded to the group given as a specific example of the alkyl group.

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

The ^{alkylene group as Y 2} and Y ³ , and the substituent on the cyclic group or the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxy group as ^{Y 6 may be linear, branched, or cyclic, or a combination thereof.} May be.

Further, the ^{alkylene group as Y 2} and Y ³ , and the alkyl group, ^{fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxy group as Y 6} may be interrupted by 1 to 3 linking groups unless the linking groups are adjacent to each other.

In addition, 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- , 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, a divalent organic group having this steroid skeleton, is -CH ₂ -CH(OH )-CH ₂ -, this alkylene group, this alkyl group, and this fluorine-containing alkyl group may be bonded to each other via a group and a bonding group adjacent to them.

In addition, 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- .

In addition, Y ¹ to Y ⁶ are each represented by 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 having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group having 1 to 18 carbon atoms is 6 to 30, e.g. For example it is 6-20.

Among these, in consideration of the vertical orientation and the coatability of the polymerizable liquid crystal, the vertical orientation group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms.

Examples of the thermally crosslinkable group include a hydroxy group, a carboxyl group, an amino group, a block isocyanate group, a vinyl group, an allyl group, an acrylic group, a methacrylic group, and an alkoxysilyl group. From the viewpoint of forming a thermosetting film at a low temperature and short time, preferable thermal crosslinking groups are a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group.

As a monomer having a hydroxy group, a carboxyl group, an amino group, and an alkoxysilyl group as a thermal crosslinkable group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, di Ethylene 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 Monomers having a hydroxy group such as -2-carboxylic-6-lactone; Acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N Monomers having a carboxyl group such as -(carboxyphenyl)acrylamide and N-(carboxyphenyl)methacrylamide; Monomers having a phenolic hydroxyl group such as hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide; Monomers having an amino group such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate; And, a monomer having an alkoxysilyl group such as acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, and methacryloyloxypropyltriethoxysilane And the like.

In addition, as long as the effects of the present invention are not impaired, when obtaining an acrylic polymer (specific copolymer) containing a vertical alignment group and a thermal crosslinkable group in the present invention, the monomer having the above-described vertical alignment group, and the thermal crosslinkable group (hydride In addition to a monomer having at least one substituent selected from a hydroxyl group, a carboxyl group, an amino group, and an alkoxysilyl group), other monomers that can be copolymerized with these monomers and do not have the above specific functional groups can be used in combination.

Specific examples of such other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitriles, maleic anhydrides, styrene compounds and vinyl compounds.

Hereinafter, specific examples of other monomers are given, but are not limited thereto.

As the acrylic acid ester compound, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycy Diyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2 -Ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, etc. are mentioned.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, and anthryl methyl methacrylate. Acrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2- Methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate And the like.

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

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

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

As described above, as a method for synthesizing a specific copolymer (acrylic copolymer having a vertical orientation group and a thermal crosslinkable group), at least one monomer selected from monomers having a vertical orientation group and a monomer having a thermal crosslinkable group are selected. It is easy to copolymerize at least one monomer to be formed and other monomers if necessary.

The amount of each monomer used to obtain a specific copolymer is based on the total amount of all monomers, 3 to 90 mol% of a monomer having a vertically oriented group, 3 to 90 mol% of a thermally crosslinkable group (hydroxy group, carboxyl group, amino group , Alkoxysilyl group), and 0 to 94 mol% of other monomers not having a specific functional group (however, the total of these monomers is 100 mol%).

When the content of the monomer having a vertical orientation group is less than 3 mol%, it is difficult to impart good vertical liquid crystal orientation. When the content of the monomer having a vertical orientation group is more than 90 mol%, the coating property of the polymerizable liquid crystal is deteriorated, and it is difficult to form a uniform retardation film.

In addition, if the content of the monomer having a thermally crosslinkable group (at least one substituent selected from a hydroxy group, a carboxyl group, an amino group and an alkoxysilyl group) is less than 3 mol%, it is difficult to impart sufficient thermosetting properties and good vertical liquid crystal orientation. Difficult to maintain

The method of obtaining the specific copolymer used in the present invention is not particularly limited, but, for example, a monomer having a vertical orientation group and a monomer having a thermal crosslinkable group, and, if necessary, a monomer not having the specific functional group, a polymerization initiator, etc. It is obtained by polymerization reaction at a temperature of 50 to 110°C in a solvent in which is coexisted. In this case, the solvent to be used is not particularly limited as long as it dissolves a monomer having a vertical orientation group, a monomer having a thermal crosslinkable group, a monomer having no specific functional group used as needed, a polymerization initiator, and the like. As the specific example, what was mentioned in the <solvent> mentioned later can be used suitably.

The specific copolymer obtained by the above method is usually in the form of a solution dissolved in a solvent. As mentioned later, the solution of the obtained specific copolymer can be used as it is as (A) component (solution of).

In addition, the solution of the specific copolymer obtained by the above method is added to diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed, followed by drying at room temperature or heating under normal pressure or reduced pressure, and specific It can be made into the powder of a copolymer. By the above operation, the polymerization initiator coexisting with the specific copolymer and the unreacted monomer can be removed, and as a result, a purified specific copolymer powder is obtained. When it is not possible to sufficiently purify in one operation, the obtained powder may be re-dissolved in a solvent, and the above operation may be repeated.

In the present invention, the specific copolymer may be used in the form of a powder or in the form of a solution obtained by re-dissolving the purified powder in a solvent to be described later.

In addition, in this invention, the specific copolymer of (A) component may be a mixture of multiple types of specific copolymers.

<(B) component>

The component (B) in the cured film forming composition of the present invention is a crosslinking agent.

It is preferable that the crosslinking agent which is (B) component is a crosslinking agent which has the functional group which can thermally crosslink of the said (A) component and a group which forms a crosslink, for example, a methylol group or an alkoxymethyl group.

Examples of the compound having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1 ,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl) )-4,5-dimethoxy-2-imidazolinone, etc. are mentioned. As a commercial item, a compound such as a glycoluril compound (trade name: CYMEL (registered trademark) 1170, POWDERLINK (registered trademark) 1174) manufactured by Nihon Cytec Industries Inc. (formerly Mitsui Cytec Ltd.), and a methylated urea resin (trade name: UFR (registered trademark)) ) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin manufactured by DIC Corporation (formerly Dainippon Ink and Chemicals, Inc.) (High condensation type, brand name: Beckamine (registered trademark) J-300S, Beckamine P-955, Beckamine N), and the like.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. As a commercial item, Nihon Cytec Industries Inc. (formerly Mitsui Cytec Ltd.) product (brand name: CYMEL (registered trademark) 1123), Sanwa Chemical Co., Ltd. product (brand name: NIKALAC (registered trademark) BX-4000, NIKALAC BX- 37, NIKALAC BL-60, NIKALAC BX-55H), etc. are mentioned.

As a specific example of an alkoxymethylated melamine, hexamethoxymethylmelamine etc. are mentioned, for example. As a commercial item, Nihon Cytec Industries Inc. (formerly Mitsui Cytec Ltd.) methoxymethyl type melamine compound (trade name: CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL 350), butoxymethyl type melamine compound (trade name : MYCOAT (registered trademark) 506, MYCOAT 508), Sanwa Chemical Co., Ltd. methoxymethyl type melamine compound (trade name: NIKALAC (registered trademark) MW-30, NIKALAC MW-22, NIKALAC MW-11, NIKALAC MS -001, NIKALAC MX-002, NIKALAC MX-730, NIKALAC MX-750, NIKALAC MX-035), butoxymethyl type melamine compound (trade name: NIKALAC (registered trademark) MX-45, NIKALAC MX-410, NIKALAC MX- 302) and the like.

Further, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound prepared from a melamine compound and a benzoguanamine compound described in U.S. Patent No. 6323310 may be mentioned. Commercially available products of the melamine compound include a brand name: CYMEL (registered trademark) 303, and the like, and as a commercial product of the benzoguanamine compound, a brand name: CYMEL (registered trademark) 1123 (above, Nihon Cytec Industries Inc. (formerly known as Nihon Cytec Industries Inc.) Mitsui Cytec Ltd.)), etc. are mentioned.

In addition, as a crosslinking agent for component (B), hydroxymethyl groups such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide (ie A polymer prepared using an acrylamide compound or a methacrylamide compound substituted with a methylol group) or an alkoxymethyl group may also be used.

Examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, And a copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide and benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight (in terms of polystyrene) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

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

The content of the crosslinking agent of the component (B) in the cured film forming composition of the present invention is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass based on 100 parts by mass of the compound as the component (A). It is ~80 parts by mass. When the content of the crosslinking agent is too small, the solvent resistance of the cured film obtained from the cured film forming composition decreases, and the vertical orientation property decreases. On the other hand, when the content is excessive, vertical orientation and storage stability may decrease.

<(C) component>

The cured film forming composition of the present invention may further contain a crosslinking catalyst as a component (C) in addition to the component (A) and the component (B).

(C) As a crosslinking catalyst which is a component, an acid or a thermal acid generator can be used suitably, for example. This component (C) is effective in accelerating the thermosetting reaction of the cured film forming composition of the present invention.

As the component (C), specifically, as the acid, a sulfonic acid group-containing compound, hydrochloric acid, or a salt thereof is mentioned. The thermal acid generator is not particularly limited as long as it is a compound that generates acid by thermal decomposition during heat treatment, that is, a compound that generates acid by thermal decomposition at a temperature of 80°C to 250°C.

Specific examples of the acid include, for example, hydrochloric acid or a salt thereof; Methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid , 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluoro Sulfonic acid group-containing compounds such as octanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, or hydrates or salts thereof And the like.

[0053]

In addition, as a compound that generates an acid by heat, for example, bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate, 1,2,3-phenylene tris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluene Sulfonic acid butyl ester, p-toluene sulfonic acid isobutyl ester, p-toluene sulfonic acid methyl ester, p-toluene sulfonic acid phenethyl ester, cyanomethyl p-toluene sulfonate, 2,2,2-trifluoroethyl p -Toluenesulfonate, 2-hydroxybutylp-toluenesulfonate, N-ethyl-p-toluenesulfonamide, further compound represented by the following formula:

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

Etc. are mentioned.

The content of the component (C) in the cured film-forming composition of the present invention is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, based on 100 parts by mass of the compound of the component (A). It is a mass part, More preferably, it is 0.5 mass part-10 mass parts. By making the content of the component (C) 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, when it is more than 20 parts by mass, the storage stability of the composition may decrease.

<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 should just be able to dissolve the (A) component, the (B) component, and if necessary, the (C) component and/or other additives to be described later, and the kind and structure thereof are not particularly limited.

Specific examples of the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol 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 One, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy -3-methylbutanoate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate , Butyl lactate, cyclopentylmethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

In the case of preparing an alignment material by forming a cured film on a resin film using the cured film forming composition of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2 -Heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. are preferable in that the resin film is a solvent exhibiting resistance.

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

<Other additives>

In addition, the cured film forming composition of the present invention, if necessary, as long as the effect of the present invention is not impaired, an adhesion improving agent, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an antioxidant. And the like.

<Preparation of cured film forming composition>

The cured film forming composition of the present invention contains the polymer of the component (A) and the crosslinking agent of the component (B), and if necessary, the crosslinking catalyst of the component (C), and the other as long as the effect of the present invention is not impaired. It is a composition that may contain additives. 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 composition for forming a cured film containing 1 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A).

[2]: A cured film-forming composition containing 1 to 100 parts by mass of the component (B) and a solvent based on 100 parts by mass of the component (A).

[3]: A cured film-forming composition containing 1 to 100 parts by mass of (B) component, 0.01 to 20 parts by mass of (C) component, and a solvent based on 100 parts by mass of the component (A).

In the case of using the cured film forming composition of the present invention as a solution, the mixing ratio, preparation method, etc. will be described in detail below.

The ratio of the solid content in the cured film forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, preferably 2% by mass to 50% It is mass %, More preferably, it is 2 mass%-20 mass %. Here, the solid content means that the solvent is removed from the total components of the cured film-forming composition.

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

In the preparation of the cured film forming composition of the present invention, a solution of a specific copolymer (polymer) obtained by polymerization reaction in a solvent can be used as it is. In this case, for example, the (B) component, further, the (C) component, and the like are added to the solution of the component (A) in the same manner as above to obtain a uniform solution. At this time, additional solvent may be added for the purpose of concentration adjustment. In this case, the solvent used in the process of producing the component (A) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.

In addition, the solution of the prepared cured film-forming composition is preferably used after filtering with a filter or the like having a pore diameter of about 0.2 μm.

<Cured film, alignment material, and retardation material>

The solution of the cured film forming composition of the present invention is applied to a substrate (for example, a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate. , ITO substrate, etc.) or film substrate (e.g., triacetyl cellulose (TAC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene Resin film such as a film), etc., by applying a bar coat, rotational coating, flow coating, roll coating, slit coating, rotational coating following the slit, inkjet coating, printing, etc. to form a coating film, and then a hot plate or By heating and drying in an oven or the like, a cured film can be formed. This cured film can be applied as it is as an orientation material.

As conditions for heating and drying, the crosslinking reaction by the crosslinking agent may proceed to such an extent that the component of the cured film (alignment material) does not elute in the polymerizable liquid crystal solution applied thereon. For example, a temperature of 60°C to 200 A heating temperature and heating time appropriately selected from the range of ℃, time from 0.4 minutes to 60 minutes are adopted. The heating temperature and heating time are preferably 70° C. to 160° C., and 0.5 minutes to 10 minutes.

The film thickness of the cured film (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 step difference and optical and electrical properties of the substrate to be 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 a vertical alignment property can be applied onto the alignment material and aligned on the alignment material. Then, by curing the retardation material in an orientation state as it is, a retardation material can be formed as a layer having optical anisotropy. And when the substrate on which the alignment material is formed is a film, it becomes useful as a retardation film.

In addition, using the two substrates having the alignment material of the present invention formed as described above, the alignment materials on the two substrates are bonded to each other through a spacer, and then a liquid crystal is injected between these substrates, and the liquid crystal is aligned. It can also be used as a liquid crystal display device.

As described above, the cured film forming composition of the present invention can be suitably used in the manufacture of various retardation materials (phase difference films) and liquid crystal display devices.

[Example]

Hereinafter, for example, the present invention will be described in more detail, but the present invention is not limited to these examples.

[Abbreviation symbols used in the examples]

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

<The polymer of (A) component and the crosslinking agent (polymer) raw material of (B) component>

LAA: lauryl acrylate

EHA: 2-ethylhexylacrylate

HEMA: 2-hydroxyethyl methacrylate

HEA: 2-hydroxyethylacrylate

MAA: methacrylic acid

MMA: methyl methacrylate

BMAA: N-butoxymethylacrylamide

AIBN: α,α'-azobisisobutyronitrile

<(B) component: crosslinking agent>

CYM303: hexamethoxymethylmelamine

<(C) component: crosslinking catalyst>

PTSA: p-toluenesulfonic acid monohydrate

<solvent>

PM: propylene glycol monomethyl ether

MIBK: isobutyl methyl ketone

The number-average molecular weight and weight-average molecular weight of the acrylic copolymer obtained according to the following synthesis example was determined by using a JASCO Corporation GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L), using the elution solvent tetrahydrofuran at a flow rate of 1 mL/min. It was measured under the condition of eluting by flowing into the column (column temperature 40°C). In addition, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.

<Synthesis Example 1>

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 content concentration of 25% by mass) (P1). Mn of the obtained acrylic copolymer was 13,300 and Mw was 27,800.

<Synthesis Example 2>

8.8 g of MAA, 14.0 g of LAA, 5.2 g of HEMA, and 0.53 g of AIBN as a polymerization catalyst were dissolved in 85.5 g of PM, and reacted at 80° C. for 16 hours to obtain an acrylic copolymer solution (solid content concentration of 25% by mass) (P2). Mn of the obtained acrylic copolymer was 11,900 and Mw was 28,800.

<Synthesis Example 3>

5.4 g of MAA, 14.0 g of LAA, 4.0 g of HEMA, and 0.37 g of AIBN as a polymerization catalyst were dissolved in 71.1 g of PM, and reacted at 80° C. for 16 hours to obtain an acrylic copolymer solution (solid content concentration of 25% by mass) (P3). Mn of the obtained acrylic copolymer was 10,800 and Mw was 25,500.

<Synthesis Example 4>

14.0 g of EHA, 2.5 g of HEA, and 0.24 g of AIBN as a polymerization catalyst were dissolved in 50.1 g of MIBK, and reacted at 80° C. for 16 hours to obtain an acrylic copolymer solution (solid content concentration of 25% by mass) (P4). Mn of the obtained acrylic copolymer was 8,900 and Mw was 20,700.

<Synthesis Example 5>

2.5 g of MAA, 9.2 g of MMA, 5.0 g of HEMA, and 0.2 g of AIBN as a polymerization catalyst were dissolved in 50.7 g of PM and reacted at 70° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration of 25% by mass) (P5). Mn of the obtained acrylic copolymer was 19,600 and Mw was 45,200.

<Synthesis Example 6>

25.0 g of BMAA and 1.04 g of AIBN as a polymerization catalyst were dissolved in 48.4 g of PM, and reacted at 85° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration of 35% by mass) (P6). Mn of the obtained acrylic copolymer was 4,800 and Mw was 3,100.

<Examples 1 to 6, Comparative Examples 1 and 2>

Each cured film forming composition of Examples 1 to 6 and Comparative Examples 1 and 2 was prepared with the composition shown in Table 1, and vertical orientation was evaluated for each.

[Table 1]

[Evaluation of vertical orientation]

Each cured film-forming composition of Examples and Comparative Examples was coated on an alkali-free glass using a spin coater for 2000 rotations and 30 seconds. Similarly, each cured film forming composition of Examples and Comparative Examples was applied on a PET film with a wet film thickness of 4 μm using a bar coater. Thereafter, heating and drying were performed in a heat circulation oven at a temperature of 80° C. for 60 seconds, respectively, to form a cured film on a glass phase and a PET film, respectively.

On this cured film, the polymerizable liquid crystal solution RMS03-015 for vertical alignment, manufactured by Merck Ltd., was applied using a bar coater with a wet film thickness of 6 µm, and left at room temperature at 23°C for 60 seconds. The coating film on this substrate was exposed at 300 mJ/cm 2 to prepare a retardation material. In addition, the polymerizable liquid crystal solution was directly coated on the glass and PET film (no cured film was formed by the cured film-forming composition), and the retardation material prepared in the same procedure was used as Comparative Example 3.

For these fabricated retardation materials, the dependence of the incidence angle of the in-plane phase difference was measured using a retardation measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. It was judged that the in-plane phase difference value at 0 degrees of incidence was 0, and that the in-plane phase difference at the incident angle of ±50 degrees was in the range of 38±5 nm was determined to be vertically aligned.

Table 2 shows the obtained results.

[Table 2]

As shown in Table 2, the retardation material using the cured film obtained from the cured film forming compositions of Examples 1 to 6 as an alignment material showed good vertical orientation regardless of the substrate used.

On the other hand, the retardation material using the cured film obtained from the cured film forming composition of Comparative Example 2 using the component (A) not containing the vertical alignment group as an alignment material did not obtain vertical alignment. In addition, the retardation material using the cured film obtained from the cured film forming composition of Comparative Example 1 as an alignment material, and the retardation material of Comparative Example 3 obtained without forming a cured film showed vertical orientation on glass but not vertical orientation on PET.

[Industrial availability]

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 of a liquid crystal display device. In particular, IPS- It is suitable as a material for optical compensation film of LCD.

Claims (8)

(A) a polymer having a vertical orientation group and a thermally crosslinkable functional group, and
(B) crosslinking agent
As a cured film forming composition containing,
The vertical orientation group is a group derived from a monomer selected from the group consisting of an alkyl ester of acrylic acid, an alkyl ester of methacrylic acid, an alkyl vinyl ether, 2-alkylstyrene, 3-alkylstyrene, 4-alkylstyrene, and N-alkylmaleimide. As, a cured film-forming composition, characterized in that the alkyl group of the monomer has 6 to 20 carbon atoms.
The method of claim 1,
(A) The composition for forming a cured film, wherein the thermally crosslinkable functional group of the component is a hydroxy group, a carboxyl group, an amino group, or an alkoxysilyl group.
The method of claim 1,
The composition for forming a cured film, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
The method of claim 1,
(C) A composition for forming a cured film further containing a crosslinking catalyst.
The method of claim 1,
(A) A cured film-forming composition containing 1 to 100 parts by mass of the component (B) based on 100 parts by mass of the component.
The method of claim 4,
(A) A cured film-forming composition containing 0.01 parts by mass to 20 parts by mass of the component (C) based on 100 parts by mass of the component.
An orientation material obtained by curing the cured film forming composition according to any one of claims 1 to 6.
A retardation material formed using a cured film obtained from the cured film forming composition according to any one of claims 1 to 6.