KR20160052545A - Cured-film-forming composition, alignment material, and phase difference material - Google Patents

Abstract

[PROBLEMS] To provide a curing film-forming composition for providing an alignment material having excellent vertical alignment property and vertically aligning a polymerizable liquid crystal with high sensitivity on a resin film and a phase difference material using such alignment material.
(A) a polymer obtained by reacting a carboxyl group of a compound having a carboxyl group and a vertically orienting group with an epoxy group of a polymer having at least one epoxy group in the side chain or terminal, (B) a crosslinking agent, and , An alignment material characterized by being obtained by using the composition, and a retardation film obtained by using the composition.

Description

CURED-FILM-FORMING COMPOSITION, ALIGNMENT MATERIAL, AND PHASE DIFFERENCE MATERIAL < RTI ID = 0.0 >

The present invention relates to a cured film forming composition suitable for a vertical alignment material for vertically orienting liquid crystal molecules. More particularly, the present invention relates to a liquid crystal display (LCD), and more particularly to an IPS liquid crystal display (In-plane Switching LCD) having a liquid crystal having a positive dielectric anisotropy (??> 0) (Positive C plate), which is used for improving the viewing angle characteristics of a liquid crystal display device (liquid crystal display device), an alignment material and a phase difference material.

The IPS-LCD is characterized by a small change in brightness / color due to a viewing angle since no vertical gradient of liquid crystal molecules occurs. It is a weak point that it is difficult to increase the contrast ratio, brightness, and response speed. For example, as disclosed in Patent Document 1, in the IPS-LCD at the initial stage of the proposal, a compensation film for viewing angle is not used, and in an IPS-LCD not using a compensation film for such a viewing angle, But exhibits a low contrast ratio value due to a 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 constitutions are shown for the liquid crystal display element described here.

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

2) More than one + A plate and + C plate are inserted in both polarizer plates.

3) The main optical axis of the + A plate is perpendicular to the main optical axis of the liquid crystal layer.

4) The retardation value R of the liquid crystal layer _LC, the retardation value of the + C plate R _{+ C,} + A plate retardation value of R ₊ is _A, and is determined so as to satisfy the food.

_RLC : R _{+ C} : R _{+ A} ? 1: 0.5: 0.25

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

Further, by minimizing the light leakage in the dark state at the inclination angle, the + A plate and the + C plate, which are intended to provide an IPS-LCD having high contrast characteristics at the front and the inclined angle and low color shift (Patent Document 3).

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

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

In addition, in the conventionally proposed vertical alignment film using polyimide, it is necessary to use a polyimide solvent such as N-methyl-2-pyrrolidone in film formation. Therefore, there is no problem with the glass substrate, but when the substrate is a film, there is a problem of damaging the substrate at the time of forming the alignment film. In addition, in a vertical alignment film using polyimide, firing at a high temperature is required, and there is a problem that the film substrate can not withstand high temperatures.

Further, a method of forming a vertical alignment film by directly treating a substrate with a silane coupling agent having a long-chain alkyl has been proposed. However, when a hydroxy group is not present on the substrate surface, the process is difficult and there is a problem that the substrate is limited (Patent Document 4).

DISCLOSURE OF THE INVENTION The present invention has been made based on the above findings and the results of the study. It is an object of the present invention to provide an optical compensation film which has excellent vertical alignment property, transparency and solvent resistance required for an optical compensation film, And to provide an alignment material capable of vertically aligning a polymerizable liquid crystal stably in a sintering condition.

Another object of the present invention is to provide an alignment material which is obtained from the above-mentioned cured film-forming composition and has an excellent vertical alignment property and which can stably orient the polymerizable liquid crystal on a resin film in a low-temperature short- And to provide a retardation material useful for a + C plate formed by using an alignment material.

As a result of intensive investigations, the present inventors have found that by selecting a cured film forming material based on an acrylic copolymer having a long chain alkyl group in its side chain, it is possible to obtain a cured And thus the present invention has been accomplished.

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

(A) a polymer obtained by reacting a carboxyl group of a compound having a carboxyl group and a vertically orienting group with an epoxy group of a polymer having at least one epoxy group in the side chain or terminal, and

(B) a crosslinking agent and (C) an acid catalyst.

Forming composition,

Wherein the vertically oriented group is a group represented by the following formula (1).

[Chemical Formula 1]

(In the formula [1]

Y ¹ represents a single bond,

Y ² represents a single bond or an alkylene group having 1 to 15 carbon atoms, or represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic group may have 1 to 3 carbon atoms 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms,

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 a steroid skeleton having 17 to 30 carbon atoms, and any hydrogen on the cyclic group An alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorinated 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 the cyclic group 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 of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine-

n represents an integer of 0 to 4, and when n is 2 or more, Y ^{5 s} 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 fluorinated 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 any one of linear, branched or cyclic, or a combination thereof However,

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 bonding groups unless the bonding groups are adjacent to each other,

In addition, Y ^2, Y ⁴ or Y ⁵ is shown a divalent cyclic or, Y ⁴ is shown a divalent organic group having a steroid skeleton or, Y ² or Y ³ is or represents an alkylene group, or Y ⁶ is an alkyl group or fluorine Containing alkyl group, the divalent organic group having a steroid skeleton, the alkylene group, the alkyl group and the fluorine-containing alkyl group may be bonded to a group adjacent thereto via a bonding group,

And the coupler is selected from the group consisting of -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO- , ≪ / RTI >

Stage, Y ² to Y ⁶ are each carbon atoms of the indicating bar 1 to 15 alkyl group, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent having a steroid skeleton organic group, carbon atom number of 1 to 18 alkyl group, a carbon atom number of The total number of carbon atoms of the fluorine-containing alkyl group of 1 to 18, the alkoxyl group of 1 to 18 carbon atoms, and the fluoro-containing alkoxyl group of 1 to 18 carbon atoms is 6 to 30).

As a second aspect, the present invention relates to a cured film forming composition according to the first aspect, wherein the polymer having at least one epoxy group in the side chain or the terminal is a polymer having a ring structure in the main chain and a number average molecular weight of 300 to 20,000.

As a third aspect, it is preferable that the polymer having at least one epoxy group in the side chain or terminal is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy Resin and a 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of a polyol. The cured film-forming composition according to the first aspect or the second aspect will be.

As a fourth aspect, the present invention relates to a cured film forming composition according to any one of the first to third aspects, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.

The fifth aspect relates to the cured film forming composition according to any one of the first to fourth aspects, which contains 1 to 100 parts by mass of the component (B) based on 100 parts by mass of the component (A).

As a sixth aspect, the present invention relates to a cured film forming composition according to any one of the first to fifth aspects, which contains (C) component in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the component (A).

As a seventh aspect, the present invention relates to an alignment material characterized by being obtained by curing the cured film-forming composition according to any one of the first to sixth aspects.

As an eighth aspect, the present invention relates to a retardation film which is formed by using a cured film obtained from the cured film-forming composition according to any one of the first to sixth aspects.

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

According to the second aspect of the present invention, it is possible to provide an alignment material having an excellent vertical alignment property and capable of vertically aligning the polymerizable liquid crystal stably in a low-temperature short-time firing condition.

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

≪ Cured film forming composition >

The cured film forming composition of the present invention comprises a polymer obtained by reacting a carboxyl group of a compound having a carboxyl group and a vertically orienting group with an epoxy group of a polymer having at least one epoxy group as a component (A) at a side chain or at a terminal thereof, A crosslinking agent and an acid catalyst as a component (C). The cured film forming composition of the present invention may contain other additives in addition to the above components (A), (B) and (C), so long as the effect of the present invention is not impaired.

Hereinafter, the details of each component will be described.

≪ Component (A) >

The component (A) contained in the cured film-forming composition of the present invention is a polymer obtained by reacting a carboxyl group of a compound having a carboxyl group and a vertically orienting group with an epoxy group of a polymer having at least one epoxy group in the side chain or terminal. In the following description, the polymer of component (A) is also referred to as a " vertically oriented polymer ".

The polymer having at least one epoxy group in the side chain or terminal may be produced by addition polymerization using an addition polymerizable monomer having an epoxy group. Alternatively, a polymer having at least one epoxy group in the side chain or terminal may be prepared by reacting a polymer having a hydroxy group with a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.

As specific examples of the polymer having at least one epoxy group in the side chain or the terminal, there may be mentioned polyglycidyl methacrylate, glycidyl methacrylate copolymer, poly (3,4-epoxycyclohexylmethyl methacrylate ), 3,4-epoxycyclohexylmethyl methacrylate copolymer. Bisphenol A type epoxy resin, bisphenol F epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, 1,2-epoxy-4- ) Cyclohexane adducts and the like.

Among these polymers having at least one epoxy group in the side chain or terminal, polymers having a ring structure in the main chain are preferable. Specific examples thereof include bisphenol A type epoxy resins, bisphenol F epoxy resins, phenol novolak type epoxy resins, Epoxy-4- (2-oxiranyl) cyclohexane adduct of a polyol and the like are preferable because the coating ability of the liquid crystal is improved.

The number average molecular weight (hereinafter referred to as number average molecular weight) in terms of polystyrene is preferably from 300 to 20,000 as the molecular weight of the polymer having at least one epoxy group in the side chain or terminal. Preferably 400 to 10,000, and more preferably 500 to 8,000.

Specific examples of the polymers having at least one epoxy group in the side chain or terminal are commercially available products such as jER 1001, jER 1002, jER 1003, jER 1004, jER 1055, jER 1007, jER 1009, jER 1010, jER 834, jER 828 (manufactured by Mitsubishi Chemical Corporation), and the like can be used as the bisphenol F type epoxy resin, jER 806, jER 807 Examples of the volatile epoxy resin include jER 152, jER 154 (manufactured by Mitsubishi Chemical Corporation), EPPN 201 and EPPN 202 (manufactured by Nippon Kayaku Co., Ltd.), and cresol novolak type epoxy resins, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), jER 80S75 (manufactured by Asahi Kasei Corporation), EOCN-102, EOCN-103S, EOCN-104S, EOCN- (Manufactured by Mitsubishi Chemical Corporation) as the bisphenol A novolak type epoxy resin, 1,2-epoxy-4- (2-oxyl Nyl) cyclohexane adduct include EHPE-3150 (manufactured by Daicel Corporation) and the like.

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

Accordingly, as the compound having a carboxyl group and a vertically oriented group, for example, a compound having a carboxyl group and a hydrocarbon group having 6 to 20 carbon atoms can be given.

Examples of the hydrocarbon group having 6 to 20 carbon atoms include straight chain, branched or cyclic hydrocarbon groups having 6 to 20 carbon atoms or aromatic groups having 6 to 20 carbon atoms.

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

(2)

In the formula [1], Y ¹ represents a single bond.

In the formula [1], Y ² represents a single bond or an alkylene group having 1 to 15 carbon atoms.

And Y ^{2 represents} a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy 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.

Examples of the heterocycle include pyrrole, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine, quinoline, pyrazoline, isoquinoline, carbazole, purine, thiadiazole, Benzothiazole ring, phenothiazine ring, oxadiazole ring, phenothiazine ring, benzothiazole ring, benzothiazole ring, benzothiazole ring, benzothiazole ring, benzothiazole ring, benzothiazole ring, Pyridine ring, pyrazine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazoline ring, pyrazoline ring, Pyrazolidine ring, triazole ring, pyrazine ring, and benzimidazole ring.

Examples of the alkyl group referred to as the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group. As the alkoxyl group, an oxygen atom- Bonded groups. Examples of the fluorine-containing alkyl group and the fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group or alkoxyl group is substituted with a fluorine atom.

Of these, Y ² is preferably a benzene ring or cyclohexane ring in view of ease of synthesis.

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

Y ⁴ in the formula [1] represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms , An alkoxyl group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.

The above-mentioned heterocyclic ring and the alkyl group referred to as a substituent may be the same as those mentioned in the above-mentioned Y ² .

Further, Y ⁴ may be a divalent organic group selected from organic groups having a steroid skeleton having 17 to 30 carbon atoms. Preferred examples thereof include cholesteryl, endostearyl (aminostearyl), β-cholestearyl, epiedostosteryl (ependodostearyl), erythrostearyl, estril, 11α-hydroxymethylstearyl , 11? -Progesteryl, laanostearyl, melatranyl (melratranyl), methyltestosteryl, norestestyl, frenenonyl,? -Cyostosteryl, stigmasteryl, testosteryl, and acetic acid A cholesterol ester, and the like. More specifically, for example, the following.

(3)

(Wherein * represents a bonding position).

Of these, 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 that it is easy to synthesize.

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 may be replaced by an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms An alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluoro-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. The above-mentioned heterocyclic ring and the alkyl group referred to as a substituent may be the same as those mentioned in Y ⁴ described above.

Among them, Y ⁵ is preferably a benzene ring or cyclohexane ring.

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

In the formula [1], 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 .

Among them, Y ⁶ is preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. More preferably, Y < ⁶ > is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. And particularly preferably, Y ⁶ is an alkoxyl group of 1-9 carbon atoms or alkyl of 1-9 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 or fluorine-containing alkoxy group mentioned in the above-mentioned formula [1] may be any one of linear, branched or cyclic, or a combination thereof.

For example, the alkyl group may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-butyl group, N-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, Butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl- Butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-butyl group, n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1 Methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, Dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3- N-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-pentyl group, Butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-n- Methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n- Hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, Ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1- Ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, An n-decyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, And the like.

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

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

Examples of the fluorine-containing alkyl group and the fluorine-containing alkoxyl group include groups in which any hydrogen atom of the alkyl group or 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 as Y ⁶ , the fluorine-containing alkyl group, the alkoxyl group and the fluorine-containing alkoxy group may be any one of linear, branched or cyclic, It is possible.

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 bonding groups unless the bonding groups are adjacent to each other.

Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group having a steroid skeleton, Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or The divalent organic group having a bivalent cyclic group, the steroid skeleton, the -CH ₂ -CH (OH) -CH ₂ -, the alkylene group, the alkyl group and the fluorine-containing alkyl group, They may be connected to adjacent groups and couplers.

The coupler may be selected from the group consisting of -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO- And -NH-CO-NH-.

On the other hand, Y ² to Y ⁶ are each carbon atoms of the indicating bar 1 to 15 alkyl group, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent having a steroid skeleton organic group, carbon atom number of 1 to 18 alkyl group, a carbon atom number of The total number of carbon atoms of the fluorine-containing alkyl group of 1 to 18, the alkoxyl group of 1 to 18 carbon atoms and the fluoro-containing alkoxyl group of 1 to 18 carbon atoms is 6 to 30, for example, 6 to 20.

Of these, the vertical aligning group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms, in consideration of the vertical alignment property and the applicability of the polymerizable liquid crystal.

Preferably, the compound having a carboxyl group and a vertically aligning group is a compound in which a carboxyl group is bonded to the vertically aligning group.

The vertically oriented polymer of component (A) in the present invention is a polymer obtained by reacting a carboxyl group of a compound having a carboxyl group and a vertically orienting group with an epoxy group of a polymer having at least one epoxy group at the side chain or at the terminal. The epoxy group and the carboxyl group react with each other to generate -CH ₂ -CH (OH) -CH ₂ - bond.

The amount of the polymer having at least one epoxy group in the side chain or terminal and the compound having a carboxyl group and the vertically orienting group for obtaining the vertically aligned polymer is preferably such that the amount of the carboxyl group and the compound having a vertically- It is preferable to use the compound having a carboxyl group and a vertically aligning group so that the carboxyl group of the compound has 5 to 60 equivalents.

When the carboxyl group of the compound having a carboxyl group and the vertically orienting group is less than 5 equivalents based on one equivalent of the epoxy having an epoxy group at one or more side chains or terminals, the desired vertical alignment property may not be sufficiently obtained in the obtained vertical alignment polymer . When the carboxyl group of the compound having a carboxyl group and the vertically aligning group is more than 60 equivalents, when a cured film (alignment material) is formed using this vertically aligned polymer and a polymerizable liquid crystal solution or the like is to be coated thereon, There is a fear that the liquid crystal molecules will be lowered (skipping of the liquid crystal).

The epoxy moiety of the polymer having at least one epoxy group at the side chain or at the terminal thereof may be reacted with a compound having a carboxyl group and a vertically orienting group without containing a vertically aligning group. In this case, the amount of the carboxyl group relative to 1 equivalent of the epoxy of the polymer having at least one epoxy group at the side chain or terminal is preferably the sum of the carboxyl group of the compound having a carboxyl group and the vertically orienting group and the carboxyl group of the compound having no carboxyl group , Preferably 5 to 60 equivalents.

The order of obtaining the vertically oriented polymer to be used in the present invention is not particularly limited. For example, a compound having at least one epoxy group at the side chain or at the terminal, a compound having a carboxyl group and a vertically aligning group, Is obtained by reacting a compound having a carboxyl group in a solvent in which a reaction catalyst and the like are coexisted at a temperature of 50 to 150 캜. Here, the solvent to be used is not particularly limited as long as it dissolves a polymer having at least one epoxy group in the side chain or terminal, a compound having a carboxyl group and a vertically orienting group, and a polymerization initiator. As specific examples thereof, mention may be made of the " solvent " which will be described later. Examples of the reaction catalyst include benzyl trimethyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyltripropyl ammonium chloride, benzyltripropyl ammonium bromide, tetramethyl ammonium chloride, Quaternary ammonium salts such as propyl ammonium chloride and tetrapropyl ammonium bromide; Quaternary phosphonium salts such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride and ethyltriphenylphosphonium bromide, and the like can be given .

The vertically oriented polymer obtained by the above method is usually in the form of a solution dissolved in a solvent. As described later, the resulting solution of the vertically oriented polymer can be used as it is as the component (A) solution.

Further, the solution of the vertically oriented polymer obtained by the above method is put into diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed. Thereafter, the solution is dried at room temperature or under reduced pressure, or heated and dried, It may be a powder of oriented polymer. By this operation, the reaction catalyst coexisting with the vertically oriented polymer and the unreacted compound can be removed, and as a result, the purified vertically oriented polymer powder can be obtained. When the powder can not be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the present invention, the vertically oriented polymer may be used in powder form or in the form of a solution in which the purified powder is redissolved in a solvent to be described later.

Further, in the present invention, the vertically oriented polymer of component (A) may be a mixture of plural kinds of vertically oriented polymers.

≪ Component (B) >

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

The crosslinking agent as the component (B) is preferably a crosslinking agent having a group capable of forming a crosslinking with the heat-crosslinkable functional group of the component (A), 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-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) (Methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis ) -4,5-dimethoxy-2-imidazolidinone. As a commercial product, 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.) (Trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation (formerly Dainippon Ink & Chemicals, Inc.) BECKMINE (registered trademark) J-300S, BECKMINE P-955, BECKMINE N), and the like can be given as examples of the urea / formaldehyde resin.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. (Trade name: CYMEL (registered trademark) 1123) manufactured by Nihon Cytec Industries Inc. (formerly Mitsui Cytec Ltd.), NIKALAC (registered trademark) BX-4000 manufactured by SANWA Chemical Co., NIKALAC BX-37, NIKALAC BL-60, and NIKALAC BX-55H).

Specific examples of the alkoxymethylated melamine include, for example, hexamethoxymethylmelamine and the like. As commercial products, methoxymethyl type melamine compounds (trade names: CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL 350) manufactured by Nihon Cytec Industries Inc. (formerly Mitsui Cytec Ltd.), butoxymethyl type melamine compounds NIKALAC MW-30, NIKALAC MW-22, NIKALAC MW (trade name) manufactured by SANWA Chemical Co., Ltd.) (Trade name: NIKALAC (registered trademark) MX-45, manufactured by NIKALAC MX-035), NIKALAC MX-001, NIKALAC MX-002, NIKALAC MX-730, NIKALAC MX- 410, NIKALAC MX-302).

A compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the 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 6,323,310 can be mentioned. CYMEL (registered trademark) 303 (manufactured by Nihon Cytec Industries, Inc. (hereinafter referred to as " CYMEL ") is commercially available as a commercially available product of the benzoguanamine compound, Mitsui Cytec Ltd.) and the like.

Furthermore, as a crosslinking agent for the component (B), there may be mentioned a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide and N-butoxymethylmethacrylamide A methylol group) or an acrylamide compound substituted with an alkoxymethyl group or a polymer prepared by using a methacrylamide compound.

Such polymers include, for example, poly (N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate, A copolymer of N-ethoxymethylmethacrylamide and benzylmethacrylate, and a copolymer of N-butoxymethylacrylamide and benzylmethacrylate and 2-hydroxypropylmethacrylate. The weight average molecular weight (polystyrene conversion value) 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 may be used alone or in combination of two or more.

The content of the crosslinking agent in 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 (parts by mass) based on 100 parts by mass of the compound (A) To 80 parts by mass. When the content of the crosslinking agent is too low, the solvent resistance of the cured film obtained from the cured film forming composition is lowered and the vertical orientation property is lowered. On the other hand, if the content is excessive, the vertical alignment property and storage stability may be deteriorated.

≪ Component (C) >

Component (C) in the cured film-forming composition of the present invention is an acid catalyst.

As the acid catalyst as the component (C), for example, an acid or a thermal acid generator may be used suitably. The component (C) is effective in promoting the thermosetting reaction of the cured film-forming composition of the present invention.

Specific examples of the component (C) include a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof as the acid. The thermal acid generator is not particularly limited as long as it is a compound which is pyrolyzed at the time of heat treatment to generate an acid, that is, a compound which is thermally decomposed at a temperature of 80 to 250 ° C to generate an acid.

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- , 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 perfluoro (2-ethoxy) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid and dodecylbenzenesulfonic acid, or hydrates or salts thereof And the like.

Examples of the compound capable of generating an acid upon exposure to heat include esters such as bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p- P-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid ethyl ester, P-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenetyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p -Toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and further compounds represented by the formula:

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

And the like.

The content of the component (C) in the cured film-forming composition of the invention is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the compound (A) Mass part, and more preferably 0.5 mass part to 10 mass parts. When the content of the component (C) is 0.01 part by mass or more, sufficient thermosetting property and solvent resistance can be imparted. However, when it is more than 20 parts by mass, the storage stability of the composition may be deteriorated.

<Solvent>

The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent to be used herein may be any solvent as long as it can dissolve the component (A), the component (B) and / or the component (C), and other additives described below that can be added if necessary. It does not.

Specific examples of the solvent include, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2- Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, But are not limited to, glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, Butanol, 2-pentanone, 2-heptanone,? -Butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, There may be mentioned ethyl acetate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, .

When a cured film-forming composition of the present invention is used and a cured film is formed on a resin film to produce an alignment material, a solvent such as methanol, ethanol, n-propanol, isopropanol, n-butanol, -Heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable in that the resin film is a solvent showing resistance.

These solvents may be used singly or in combination of two or more.

<Other additives>

The cured film-forming composition of the present invention may further contain additives such as adhesion improvers, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, oxidizing agents And the like.

&Lt; Preparation of cured film forming composition >

The cured film-forming composition of the present invention contains the vertically oriented polymer of component (A), the crosslinking agent of component (B) and / or the acid catalyst of component (C) and further impairs the effect of the present invention Or other additives unless otherwise specified. Normally, 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 1 part by mass 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 part by mass 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 a solvent and a component (C) in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the component (A).

[4] A cured film-forming composition comprising a component (B), from 0.01 to 20 parts by mass of a component (C), and a solvent in an amount of 1 part by mass to 100 parts by mass based on 100 parts by mass of the component (A).

The mixing ratio, preparation method and the like when the cured film forming composition of the present invention is used as a solution will be described in detail below.

The proportion of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent, but it is preferably 1% by mass to 60% by mass, and more preferably 2% Mass%, and more preferably 2 mass% to 20 mass%. Here, the solid content refers to the solvent excluding the entire components of the cured film forming composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method in which a solution of the component (A) dissolved in a solvent is mixed with the component (B) and / or the component (C) at a predetermined ratio to prepare a homogeneous solution, In the appropriate step, other additives may be further added and mixed as required.

In the preparation of the cured film-forming composition of the present invention, the solution of the vertically oriented polymer obtained by the reaction in a solvent can be used as it is. In this case, for example, the component (B) and / or the component (C) are added to the solution of the component (A) in the same manner as described above to obtain a homogeneous solution. At this time, additional solvent may be added for the purpose of concentration adjustment. At this time, the solvent used in the production of the component (A) may be the same as or different from the solvent used for adjusting the concentration of the cured film forming composition.

It is preferable that the prepared solution of the cured film-forming composition is filtered after using a filter having a pore diameter of about 0.2 mu m or the like.

<Cured film, alignment material and retardation material>

The solution of the cured film-forming composition of the present invention may be applied to a substrate (e.g., a substrate coated with a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum, chromium, , An ITO substrate, etc.) or a film substrate (for example, a triacetyl cellulose (TAC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer (COC) film, a polyethylene terephthalate (PET) film, A spin coating, a slit coating, a slit coating, a spin coating, an ink jet coating, a printing, or the like, to form a coating film on a hot plate or a resin film By heating and drying in an oven or the like, a cured film can be formed. This cured film can be applied as an alignment material as it is.

As the conditions of the heating and drying, a crosslinking reaction by the crosslinking agent proceeds so that the component of the cured film (alignment material) does not elute into the polymerizable liquid crystal solution applied thereon. For example, Lt; 0 &gt; C, and a heating time and a heating time appropriately selected within a range of from 0.4 minute to 60 minutes. The heating temperature and heating time are preferably 70 ° C to 160 ° C for 0.5 minute 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 to 5 占 퐉 and can be appropriately selected in consideration of the step difference of the substrate to be used and the optical and electrical properties.

Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a phase difference material such as a polymerizable liquid crystal solution having vertical orientation can be coated on the alignment material and aligned on the alignment material. The phase difference material can be formed as a layer having optically anisotropic properties by irradiating ultraviolet rays of 300 to 400 nm and curing the phase difference material in the aligned state. When the substrate on which the alignment material is formed is a film, it is useful as a retardation film.

Further, two substrates having the alignment material of the present invention formed as described above are used, and the alignment materials on the two substrates face each other through the spacer, liquid crystal is injected between these substrates, May be used as the liquid crystal display element.

Thus, the cured film-forming composition of the present invention can be suitably used for the production of various retardation films (phase difference films) and liquid crystal display devices.

Example

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

[Abbreviation used in the examples]

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

<Cross-linking agent (polymer) raw material of the vertically oriented polymer of component (A) and component (B)

jER-1001: bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation molecular weight 900

jER-1055: Bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation Molecular weight 1,600

jER-157S70: epoxidized bisphenol A novolak resin manufactured by Mitsubishi Chemical Corporation

ECN-1299: Asahi Kasei Corporation Cresol novolac resin

EHPE-3150: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of trimethylolpropane manufactured by Daicel Corporation

LAUA: Lauric acid

5CCA: 4'-Pentyl- (1,1'-bicyclohexane) -4-carboxylic acid

BMAA: N-butoxymethyl acrylamide

BTEAC: Benzyltriethylammonium chloride

AIBN: α, α'-azobisisobutyronitrile

&Lt; Component (B): Crosslinking agent >

CYM303: hexamethoxymethyl melamine

&Lt; Component (C): acid catalyst >

PTSA: p-toluenesulfonic acid monohydrate

<Solvent>

PM: Propylene glycol monomethyl ether

MIBK: isobutyl methyl ketone

The number-average molecular weight and the weight-average molecular weight of the acrylic copolymer obtained according to the following Synthesis Examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation and eluting solvent tetrahydrofuran at a flow rate of 1 mL / min (Column temperature: 40 占 폚) and eluted. On the other hand, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed as polystyrene conversion values.

&Lt; Synthesis Example 1 &

50.0 g of jER-1001, 6.25 g of LAUA and 0.14 g of BTEAC were dissolved in 131.58 g of PM and reacted at 110 DEG C for 16 hours to obtain a vertically oriented polymer (solid content concentration 30 mass%) (P1). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the epoxy group disappeared as the LAUA all reacted.

&Lt; Synthesis Example 2 &

50.0 g of jER-1055, 3.54 g of LAUA and 0.079 g of BTEAC were dissolved in 125.0 g of PM and reacted at 110 占 폚 for 16 hours to obtain a vertically oriented polymer (solid content concentration 30 mass%) (P2). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the epoxy group disappeared as the LAUA all reacted.

&Lt; Synthesis Example 3 &

50.0 g of jER-157S70, 14.3 g of LAUA and 0.33 g of BTEAC were dissolved in 150.8 g of PM and reacted at 110 DEG C for 16 hours to obtain a vertically oriented polymer (solid concentration 30% by mass) (P3). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the epoxy group disappeared as the LAUA all reacted.

&Lt; Synthesis Example 4 &

50.0 g of ECN-1299, 14.0 g of LAUA and 0.32 g of BTEAC were dissolved in 150.2 g of PM and reacted at 110 占 폚 for 16 hours to obtain a vertically oriented polymer (solid concentration 30% by mass) (P4). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the epoxy group disappeared as the LAUA all reacted.

&Lt; Synthesis Example 5 &

50.0 g of EHPE-3150, 5.59 g of LAUA and 0.036 g of BTEAC were dissolved in 129.8 g of PM and reacted at 110 占 폚 for 16 hours to obtain a vertically oriented polymer (solid content concentration 30 mass%) (P5). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the epoxy group disappeared as the LAUA all reacted.

&Lt; 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 DEG C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 35 mass%) (P6). The obtained acrylic copolymer had Mn of 4,800 and Mw of 3,100.

&Lt; Synthesis Example 7 &

50.0 g of EHPE-3150, 24.4 g of 5CCA and 0.49 g of BTEAC were dissolved in 174.7 g of PM and reacted at 110 DEG C for 16 hours to obtain a vertically oriented polymer (solid concentration 30% by mass) (P7). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the epoxy group disappeared as the 5CCA all reacted.

&Lt; Examples 1 to 7, Comparative Examples 1 and 2 >

Each of the cured film forming compositions of Examples 1 to 7 and Comparative Examples 1 and 2 was prepared with the composition shown in Table 1, and the vertical alignability was evaluated for each of them.

[Table 1]

[Evaluation of vertical orientation]

Each of the cured film forming compositions of Examples and Comparative Examples was coated on alkali-free glass at 2000 rotations for 30 seconds using a spin coater. Similarly, each of the cured film forming compositions of Examples and Comparative Examples was applied on a PET film with a wet film thickness of 4 占 퐉 using a bar coater. Thereafter, they were heated and dried in a thermo-circulating oven at a temperature of 100 DEG C for 60 seconds to form a cured film on the glass and PET film, respectively.

On this cured film, a polymerizable liquid crystal solution for homeotropic alignment RMS03-015 made by Merck KGaA was applied by a bar coater to a wet film thickness of 6 占 퐉 and left at a room temperature of 23 占 폚 for 60 seconds. The coating film on the substrate was exposed at 300 mJ / cm 2 to prepare a retardation film. On the other hand, the polymerizable liquid crystal solution was directly applied onto the glass and PET film (no cured film was formed by the cured film-forming composition), and the retardation produced in the same procedure was set as Comparative Example 3. [

The produced retardation material was measured for the incident angle dependency of the in-plane retardation using RETS100, a phase difference measuring apparatus manufactured by Otsuka Electronics Co., Ltd. The in-plane retardation value at 0 degree and the in-plane retardation at the incident angle of +/- 50 degrees in the range of 38 +/- 5 nm were determined to be vertically aligned.

The obtained results are shown in Table 2.

[Evaluation of Liquid Crystalline Coating]

Each of the cured film forming compositions of Examples and Comparative Examples was applied to a PET film with a wet film thickness of 4 占 퐉 using a bar coater. Thereafter, heating and drying were carried out in a thermocycling oven at a temperature of 100 DEG C for 60 seconds to form a cured film on the PET film.

On this cured film, a polymerizable liquid crystal solution for homeotropic alignment RMS03-015 made by Merck KGaA was applied by a bar coater to a wet film thickness of 6 占 퐉 and left at a room temperature of 23 占 폚 for 60 seconds. The coating film on the substrate was exposed at 300 mJ / cm 2 to prepare a retardation film. On the other hand, the polymerizable liquid crystal solution was applied directly onto the PET film (no cured film was formed by the cured film forming composition), and the retardation film produced in the same procedure was regarded as Comparative Example 3.

This retardation material was visually observed, and it was judged that the liquid crystal fogging was good when pinholes were not generated due to the liquid crystal bouncing.

The obtained results are shown in Table 2.

[Table 2]

As shown in Table 2, all of the retardation materials using the cured film obtained from the cured film-forming composition of Examples 1 to 7 as an alignment material exhibited good vertical alignability regardless of the substrate used, and the liquid crystal application properties were also good.

On the other hand, a retardation film using a cured film obtained from the cured film-forming composition of Comparative Example 1 which did not contain both the crosslinking agent (B) and the acid catalyst (C) as an aligning agent, The phase difference material using the cured film obtained from the cured film-forming composition of Comparative Example 2 as an alignment material did not have vertical alignment property.

In addition, the retardation of Comparative Example 3 obtained without forming a cured film showed vertical alignment in the glass phase, but no vertical orientation in the 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 element or an optically anisotropic film provided inside or outside the liquid crystal display element, As a material for an optical compensation film of an LCD.

Claims (8)

(A) a polymer obtained by reacting a carboxyl group of a compound having a carboxyl group and a vertically orienting group with an epoxy group of a polymer having at least one epoxy group in the side chain or terminal, and
(B) a crosslinking agent and (C) an acid catalyst.
Forming composition,
Wherein the vertically oriented group is a group represented by the following formula (1).
[Chemical Formula 1]

(In the formula [1]
Y ¹ represents a single bond,
Y ² represents a single bond or an alkylene group having 1 to 15 carbon atoms, or represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and any hydrogen atom on the cyclic group may have 1 to 3 carbon atoms 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms,
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 a steroid skeleton having 17 to 30 carbon atoms, and any hydrogen on the cyclic group An alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorinated 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 the cyclic group 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 of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine-
n represents an integer of 0 to 4, and when n is 2 or more, Y ^{5 s} 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 fluorinated 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 as Y ⁶ , the fluorine-containing alkyl group, the alkoxyl group and the fluorine-containing alkoxy group may be any of linear, branched or cyclic, However,
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 bonding groups unless the bonding groups are adjacent to each other,
In addition, Y ^2, Y ⁴ or Y ⁵ is shown a divalent cyclic or, Y ⁴ is shown a divalent organic group having a steroid skeleton or, Y ² or Y ³ is or represents an alkylene group, or Y ⁶ is an alkyl group or fluorine Containing alkyl group, the divalent organic group having a steroid skeleton, the alkylene group, the alkyl group and the fluorine-containing alkyl group may be bonded to a group adjacent thereto via a bonding group,
And the coupler is selected from the group consisting of -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO- And -NH-CO-NH-,
Stage, Y ² to Y ⁶ are each carbon atoms of the indicating bar 1 to 15 alkyl group, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent having a steroid skeleton organic group, carbon atom number of 1 to 18 alkyl group, a carbon atom number of The total number of carbon atoms of the fluorine-containing alkyl group of 1 to 18, the alkoxyl group of 1 to 18 carbon atoms, and the fluoro-containing alkoxyl group of 1 to 18 carbon atoms is 6 to 30).
The method according to claim 1,
Wherein the polymer having at least one epoxy group in the side chain or the terminal is a polymer having a ring structure in the main chain and a number average molecular weight of 300 to 20,000.
3. The method according to claim 1 or 2,
Wherein the polymer having at least one epoxy group in the side chain or terminal is selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, , And 2-epoxy-4- (2-oxiranyl) cyclohexane adduct.
4. The method according to any one of claims 1 to 3,
Wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
5. The method according to any one of claims 1 to 4,
(B) is contained in an amount of 1 part by mass to 100 parts by mass based on 100 parts by mass of the component (A).
6. The method according to any one of claims 1 to 5,
(C) component in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the component (A).
An alignment material obtained by curing the cured film-forming composition according to any one of claims 1 to 6.
A retardation film which is formed by using a cured film obtained from the cured film forming composition according to any one of claims 1 to 6.