TWI653285B - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

An object of the present invention is to provide a cured film forming composition for providing an alignment material having excellent vertical alignment properties and capable of vertically aligning a polymerizable liquid crystal with high sensitivity even on a resin film, and using the alignment material. Phase difference material.

The present invention provides a cured film forming composition comprising (A) reacting a carboxyl group of a compound having a carboxyl group and a vertical alignment group with an epoxy group of a polymer having one or more epoxy groups at a side chain or a terminal group. a polymer, and at least one compound selected from the group consisting of (B) a crosslinking agent and (C) an acid catalyst, thereby providing an alignment material obtained by using the composition, and a phase difference material, The characteristics are obtained by using the composition.

Description

Hardened film forming composition, alignment material and phase difference material

The present invention relates to a cured film forming composition of a vertical alignment material suitable for vertically aligning liquid crystal molecules. In particular, the present invention relates to an IPS liquid crystal display device (In-plane) for improving a liquid crystal display (LCD), specifically, a liquid crystal (Δε>0) filled with positive dielectric anisotropy. Switching LCD; In-plane alignment switching LCD) The +C plate (positive C plate) is used to form a composition, a alignment material, and a phase difference material.

The IPS-LCD has a feature that the luminance change/color change due to the viewing angle is small because the tilt of the liquid crystal molecules does not occur in the vertical direction, but the weak points are that the contrast, the brightness, and the response speed are not easily improved. For example, as disclosed in Patent Document 1, the IPS-LCD in the initial stage of the proposal does not use the compensation film of the viewing angle, and therefore the IPS-LCD which does not use the compensation film of the viewing angle has a relatively large light leakage in the dark state of the tilt angle, so The disadvantage of displaying low contrast values.

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

1) A liquid crystal layer having a horizontal alignment is sandwiched between two substrates supplied by electrodes for applying a parallel electric field to the liquid crystal layer.

2) Clamp more than one +A plate and +C plate in the two polarizing plates.

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

4) The liquid crystal layer retardation value R _LC, + C plate retardation value of R _{+ C, +} A-plate retardation value of R _{+ A} of the system to satisfy the following formula decided.

R _LC :R _+C :R _+A ≒1:0.5:0.25

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

Moreover, based on the provision of an IPS-LCD having a high contrast characteristic with a front side and a tilt angle and a low color shift by minimizing the light leakage of the dark state of the tilt angle, it is disclosed that the +A board is +C board IPS-LCD (Patent Document 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 2-256023

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-133408

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-122715

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2001-281669

As proposed in the past, the +C plate is very useful as an optical compensation film for IPS-LCD because it can compensate for light leakage when the viewing angle of the polarizing plate is large. However, it has been conventionally known that it is difficult to exhibit vertical alignment (+C plate) by the method of extension processing.

Further, in the conventional vertical alignment film using polyimine, it is necessary to use a solvent of a polyimine such as N-methyl-2-pyrrolidone for film production. Therefore, there is no problem with the glass substrate, but when the substrate is a film, there is a problem that the substrate is damaged when the alignment film is formed. Moreover, when a vertical alignment film using polyimine is required to be fired at a high temperature, there is a problem that the film substrate is not resistant to high temperatures.

Further, a method of directly treating a substrate with a decane coupling agent having a long-chain alkyl group or the like to form a vertical alignment film has been proposed, but it is difficult to handle when a hydroxyl group is not present on the surface of the substrate, and the substrate is limited. Problem (Patent Document 4)

The present invention has been completed based on the above findings or review results, and the problem to be solved is to provide a cured film forming composition for providing excellent vertical alignment while having the transparency required for an optical compensation film or Solvent resistance, and the firing conditions on the resin film at a low temperature for a short period of time are also stable and the alignment of the polymerizable liquid crystal can be aligned.

Moreover, another object of the present invention is to provide a phase difference A material obtained by forming a composition of the above-mentioned cured film, having excellent vertical alignment property, and being used for an alignment material which is stable in a short-time firing condition on a resin film at a low temperature and which can vertically align a polymerizable liquid crystal. And a +C plate formed using the alignment material.

As a result of repeating the positive review for achieving the above object, the present inventors have found that by selecting a cured film forming material having a long-chain alkyl group-containing acrylic copolymer as a base, it is possible to form an excellent vertical regardless of the type of the substrate. The oriented hardened film thus completes the present invention.

That is, the first aspect of the present invention is a cured film forming composition characterized by comprising a cured film forming composition of the following components: (A) a carboxyl group of a compound having a carboxyl group and a vertical alignment group for a side chain or an end a polymer which reacts with an epoxy group of a polymer having one or more epoxy groups, and at least one compound selected from the group consisting of (B) a crosslinking agent and (C) an acid catalyst, and the aforementioned vertical alignment property The base system is represented by the following 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 a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring. And any hydrogen atom on the above cyclic group may pass through 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, and 1 carbon atom ~3 is substituted by a fluorine-containing alkoxy group or a fluorine atom, Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y ⁴ represents a single bond, or represents a benzene ring, a cyclohexane ring or a heterocyclic ring. a divalent cyclic group or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, and any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms and 1 carbon atom a alkoxy group of ~3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ represents a benzene ring, a cyclohexane ring or a heterocyclic ring a bivalent cyclic group selected, wherein any hydrogen atom on the cyclic group may pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. An alkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n represents an integer of 0 to 4, n Is 2 or more, Y ⁵ may be the same or different from each other, Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, the fluorine-containing alkyl group, the number of carbon atoms of 1 to 18 carbon atoms, alkoxy of 1 to 18 oxygen a fluoroalkoxy group having 1 to 18 carbon atoms, an alkylene group of Y ² and Y ³ , a substituent on the cyclic group or an alkyl group of Y ⁶ , a fluorine-containing alkyl group, an alkoxy group and the like The fluoroalkoxy group may be any of a linear chain, a branched chain or a cyclic group, or a combination thereof, and an alkylene group of Y ² and Y ³ , and an alkyl group of Y ⁶ , a fluorine-containing alkyl group, an alkoxy group. The group and the fluorine-containing alkoxy group may be interrupted by 1 to 3 bonding groups as long as the bonding groups are not adjacent to each other, and further Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a steroid. a divalent organic group of the skeleton, or Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having a steroid skeleton, and the extension The alkyl group, the alkyl group and the fluorine-containing alkyl group may also be bonded to the group adjacent to the bonding group, and the above bonding group is represented by -O-, -CH ₂ O-, -CO-, Groups consisting of -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH- Group, however, the number of carbon atoms, Y ² to Y ⁶ each represent an extension of the alkyl group having 1 to 15, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton of carbon atoms of 1 to 18 The total number of carbon atoms of the alkyl group, the fluorine-containing alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, and the fluorine-containing alkoxy group having 1 to 18 carbon atoms is 6 to 30).

The cured film formation composition according to the first aspect, wherein the polymer having one or more epoxy groups in the side chain or the terminal has a number average molecular weight of 300 to 20,000 having a ring structure on the main chain. .

The third aspect is the cured film forming composition according to the first aspect or the second aspect, wherein the side chain or the polymer having one or more epoxy groups at the terminal is a bisphenol A type epoxy resin or a bisphenol F. Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin and polyol 1,2-epoxy-4-(2-epoxy) Any polymer selected from the group consisting of ethyl)cyclohexane adducts.

The fourth viewpoint is described in any one of the first to third aspects. The cured film forms a composition in which the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.

The cured film forming composition according to any one of the first aspect to the fourth aspect, wherein the component (B) is contained in an amount of from 1 part by mass to 100 parts by mass based on 100 parts by mass of the component (A).

The cured film formation composition according to any one of the first aspect to the fifth aspect, wherein the component (C) is contained in an amount of from 0.01 part by mass to 20 parts by mass based on 100 parts by mass of the component (A).

The seventh aspect is a aligning material obtained by curing the cured film forming composition according to any one of the first aspect to the sixth aspect.

The eighth aspect is a phase difference material which is formed by using a cured film obtained by forming a composition of the cured film described in any one of the first aspect to the sixth aspect.

According to the first aspect of the present invention, it is possible to provide a cured film forming composition which can be used to provide excellent vertical alignment, which can be stabilized even at a low temperature for a short time on a resin film, and can be made of a polymerizable liquid crystal. Vertical alignment of the alignment material.

According to the second aspect of the present invention, it is possible to provide an alignment material which has excellent vertical alignment properties and which is stable under low-temperature firing conditions and which can vertically align the polymerizable liquid crystal.

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

<hardened film forming composition>

The cured film of the present invention comprises a polymer having a composition in which the carboxyl group of the compound having a carboxyl group and a vertical alignment group is reacted with an epoxy group of a polymer having a carboxyl group and a vertical alignment group as a side chain or a polymer having one or more epoxy groups at the terminal. And at least one compound selected from the group consisting of a crosslinking agent of the component (B) and an acid catalyst of the 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) as long as the effects of the present invention are not impaired.

Hereinafter, each component will be described in detail.

<(A) component>

The component (A) contained in the cured film formation composition of the present invention reacts a carboxyl group of a compound having a carboxyl group and a vertical alignment group with an epoxy group of a polymer having one or more epoxy groups at a side chain or a terminal. polymer. Further, in the following description, the polymer of the component (A) is also referred to as "vertical alignment polymer".

A polymer having one or more epoxy groups in a side chain or a terminal can be produced by addition polymerization using an addition polymerizable monomer having an epoxy group. Alternatively, a polymer having one or more epoxy groups in a side chain or a terminal may be a polymer compound having a hydroxy acid group and epichlorohydrin, glycidyl group It is produced by reacting a compound having an epoxy group such as a benzenesulfonate.

Specific examples of the polymer having one or more epoxy groups in the side chain or the terminal are exemplified by, for example, polyglycidyl methacrylate, glycidyl methacrylate copolymer, and poly(3,4-epoxy ring of methacrylic acid). Hexylmethyl ester), 3,4-epoxycyclohexylmethyl methacrylate copolymer, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolac type Epoxy resin, bisphenol A novolac type epoxy resin, trimethylolpropane 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct, and the like.

Among the polymers having one or more epoxy groups at the side chain or terminal, a polymer having a ring structure in the main chain is preferred, and specifically, bisphenol is used in view of improving the coatability of the liquid crystal. A type epoxy resin, bisphenol F epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, polyol 1,2-epoxy group A -4-(2-epoxyethyl)cyclohexane adduct or the like is preferred.

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

A commercially available product may be suitably used as the polymer having one or more epoxy groups at the side chain or the terminal. Specific examples of the bisphenol A type epoxy resin may be listed as jER1001, jER1002, jER1003, jER1004, jER1055, jER1007, and jER1009. , jER1010, jER834, jER828 (the above is Mitsubishi Chemical Co., Ltd.), etc., bisphenol F type epoxy resin can be listed as jER806, jER807 (above is Mitsubishi Chemical Corporation) Manufacture of phenol novolac type epoxy resin, such as jER152, jER154 (above is Mitsubishi Chemical Co., Ltd.), EPPN201, EPPN202 (above, manufactured by Nippon Kayaku Co., Ltd.), cresol novolac type resin Examples are ECN-1299 (Asahi Kasei Co., Ltd.), EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above is Nippon Chemical Co., Ltd.), jER80S75 ( Mitsubishi Chemical Co., Ltd., etc., bisphenol A novolac type epoxy resin can be exemplified by jER157S70 (manufactured by Mitsubishi Chemical Corporation), etc., 1,2-epoxy-4-(2-epoxy) of polyol The ethylenyl cyclohexane adduct is exemplified by EHPE-3150 (manufactured by Daicel Co., Ltd.).

In the present specification, the vertical alignment group means a group containing a hydrocarbon group having a carbon number of about 6 to 20, and specifically means a group represented by the formula [1] described later.

Thus, examples of the compound having a carboxyl group and a vertical alignment group include a compound having a carboxyl group and a hydrocarbon group having about 6 to 20 carbon atoms.

The hydrocarbon group having 6 to 20 carbon atoms is exemplified by a linear, branched or cyclic alkyl group having 6 to 20 carbon atoms or a hydrocarbon group having 6 to 20 carbon atoms having an aromatic group.

The vertical alignment group is more specifically a group represented by the following formula [1].

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 exemplifies a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may pass through an alkyl group having 1 to 3 carbon atoms and 1 to 1 carbon atom. 3 alkoxy group, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom.

The above heterocyclic ring is a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, an oxazole ring, an anthracene ring, and a thiazide. Oxazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazosin ring, triazole ring, piperidine ring, benzimidazole ring, porphyrin ring, phenanthroline ring, anthracene ring, quinoxaline a ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, etc., more preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, an indazole ring, A pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazosin ring, a triazole ring, a piperidine ring, a benzimidazole ring.

The alkyl group as the above-mentioned substituent is exemplified by a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a cyclopropyl group, and the above alkoxy group may be exemplified by the above-mentioned alkyl group as a specific example of the above-mentioned alkyl group. The oxygen atom is O-based. Further, the fluorine-containing alkyl group or the fluorine-containing alkoxy group may be a group in which any one of the alkyl group and the alkoxy group is substituted with a fluorine atom.

Among these, Y ^{2 is} preferably a benzene ring or a cyclohexane ring from the viewpoint of easy synthesis.

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

In the above formula [1], Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may have a carbon number of 1 An alkyl group of ~3, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom.

The above heterocyclic ring and the alkyl group as a substituent may be exemplified by the above Y ² .

Further, Y ⁴ may be a divalent organic group selected from an organic group having a steroid skeleton having 17 to 30 carbon atoms. Preferred examples thereof are those selected from the group consisting of cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, ergosteryl, and estradiol. 11α-hydroxymethylstearyl, 11α-progesteryl, lanosteryl, meratranyl, methyltestosteryl, desmethyl dehydrogenation The structure of norethisteryl, pregnenol, beta-sterosteryl, stigmasteryl, testosteryl, and cholesteryl acetate removes two hydrogen atoms. The two-valent base of the structure. More specifically, for example, the following.

(where * indicates the bond position). Among 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 from the viewpoint of easy synthesis.

In the formula [1], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms or carbon. The alkoxy group having 1 to 3 atomic atoms, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted. The above heterocyclic ring, an alkyl group or the like as a substituent may be listed in the above Y ⁴ .

Among these, Y ^{5 is} preferably a benzene ring or a cyclohexane ring.

In the formula [1], n represents an integer of 0 to 4, and when n is 2 or more, the groups in which Y ⁵ may be the same may be different groups. Among them, n is preferably from 0 to 3 from the viewpoint of availability of raw materials or ease of synthesis. Better is 0~2.

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 alkoxy group having 1 to 18 carbon atoms or a carbon number of 1~. 18 fluoroalkoxy.

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 alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 10 carbon atoms. Oxygen. More preferably, Y ⁶ is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Preferably, Y ⁶ is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

Further, when Y ⁴ is a divalent organic group having a steroid skeleton, Y ^{6 is} preferably a hydrogen atom.

The alkylene group, the alkyl group, the fluorine-containing alkyl group, the alkoxy group or the fluorine-containing alkoxy group exemplified in the above formula [1] may be any one of a linear chain, a branched chain or a cyclic group or the like. combination.

For example, the above alkyl group is exemplified by, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl Base, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl Base-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl , 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl Base, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl -1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-positive 1,1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2,2-dimethyl-n-pentyl, 2,3-Dimethyl-n-pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl , 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2- Ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3- Base-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n-hexyl, 1,3-dimethyl-n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-Dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl 1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl Base, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, N-tridecyl, n-tetradecyl, n-pentadecyl and the like.

The alkylene group may be a divalent group obtained by removing one arbitrary hydrogen atom from the alkyl group.

The alkoxy group may be a group in which an oxygen atom -O- is bonded to the group as a specific example of the alkoxy group.

Further, the fluorine-containing alkyl group or the fluorine-containing alkoxy group may be a group in which any one of the alkyl group and the alkoxy group is substituted with a fluorine atom.

The alkylene group of the above 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 alkoxy group and the fluorine-containing alkoxy group may be linear or branched. Or one of the rings or a combination of these.

Further, the alkylene group as Y ² and Y ³ and the alkyl group, fluorine-containing alkyl group, alkoxy group and fluorine-containing alkoxy group as Y ⁶ may be one to three as long as the bonding groups are not adjacent to each other. The key node is interrupted.

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

And the above bonding group is represented by -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO The group selected from the group consisting of -NH- and -NH-CO-NH-.

Further, Y ² to Y ⁶ each represent an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton, and an alkyl group having 1 to 18 carbon atoms. The total number of carbon atoms of the fluorine-containing alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, and the fluorine-containing alkoxy group having 1 to 18 carbon atoms is 6 to 30, for example, 6~. 20.

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

Preferably, the compound having a carboxyl group and a vertical alignment group is a compound in which a carboxyl group is bonded to the above-mentioned vertical alignment group.

In the present invention, the vertical alignment polymer of the component (A) is obtained by reacting a carboxyl group of a compound having a carboxyl group and a vertical alignment group with an epoxy group of a polymer having one or more epoxy groups at the side chain or terminal group. polymer. By the reaction of the epoxy group with a carboxyl group, a bond such as -CH ₂ -CH(OH)-CH ₂ - is formed.

A compound having a carboxyl group and a vertical alignment group, and a compound having a carboxyl group and a vertical alignment group, preferably having a side chain or a terminal group of the above-mentioned vertical alignment polymer, is preferably used to give a compound having a carboxyl group and a vertical alignment group. The carboxyl group is used in an amount of 5 to 60 equivalents per 1 equivalent of the epoxy group of the polymer having one or more epoxy groups in the side chain or the terminal.

When the epoxy group of the polymer having one or more epoxy groups in the side chain or the terminal is 1 equivalent, and the carboxyl group of the compound having a carboxyl group and a vertical alignment group is less than 5 equivalents, the obtained vertical alignment polymer may not be sufficient. Obtain the desired vertical alignment. Further, when the carboxyl group of the compound having a carboxyl group and a vertical alignment group exceeds 60 equivalents, a cured film (orienting material) is formed using the vertical alignment polymer, and liquid crystal coating is applied when a polymerizable liquid crystal solution or the like is applied thereon. The decline in sex (the liquid crystal does not get stuck).

Also, it is also possible to react with a compound having a carboxyl group and a vertical alignment group. The epoxy residue of the polymer having one or more epoxy groups at the side chain or the terminal is reacted with a compound having a carboxyl group without a vertical alignment group. In this case, the amount of the carboxyl group is 1 equivalent to the epoxy group of the polymer having one or more epoxy groups in the side chain or the terminal, and the carboxyl group of the compound having a carboxyl group and a vertical alignment group does not contain a vertical alignment group. The total amount of the carboxyl groups of the compound having a carboxyl group is preferably from 5 to 60 equivalents.

The order of obtaining the vertical alignment polymer used in the present invention is not particularly limited, and for example, a polymer having one or more epoxy groups in a side chain or a terminal, a compound having a carboxyl group and a vertical alignment group, and optionally, The compound having a carboxyl group as a vertical alignment group is obtained by reacting at a temperature of 50 to 150 ° C in a solvent in which a reaction catalyst or the like is present. In this case, the solvent to be used is not particularly limited as long as it is a polymer having one or more epoxy groups in a side chain or a terminal, a compound having a carboxyl group and a vertical alignment group, and a polymerization starting agent. Specific examples thereof can be referred to as those described in <Solvents> which will be described later. The reaction catalysts are benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride. a quaternary ammonium salt such as benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride or tetrapropylammonium bromide; tetraphenylphosphonium chloride; Tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, and the like, and an onium salt.

The vertically aligned polymer obtained by the aforementioned method is usually in the form of a solution dissolved in a solvent. As will be described later, the solution of the obtained vertically-oriented polymer can be directly used as the (component) (A) solution.

Further, the solution of the vertically aligned polymer obtained by the above method is poured into diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered. After washing, it is heated at normal pressure or reduced pressure. Drying or heating and drying can be a powder of a vertically aligned polymer. By the foregoing operation, the reaction catalyst and the unreacted catalyst coexisting with the vertically aligned polymer can be removed, and as a result, the powder of the purified vertically aligned polymer can be obtained. When the primary operation is not sufficiently purified, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.

In the present invention, the vertical alignment polymer may be used in the form of a powder, or may be used in the form of a solution obtained by redissolving the purified powder in a solvent to be described later.

Further, in the present invention, the vertically-aligned polymer of the component (A) may also be a mixture of a plurality of vertically-aligned polymers.

<(B) component>

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

The crosslinking agent of the component (B) is preferably a group having a crosslinking group which can form a crosslinking with the thermally crosslinkable functional group of the above component (A), for example, a crosslinking agent having a methylol group or an alkoxymethyl group. The compound having such a group is exemplified by a methylol compound such as an alkoxymethylated glycol urea, an alkoxymethylated benzoquinone or an alkoxymethylated melamine.

Specific examples of the alkoxymethylated glycol urea are, for example, 1,3,4,6-fluorene (methoxymethyl)glycol urea, 1,3,4,6-fluorene (butoxyl) Glycol urea, 1,3,4,6-indole (hydroxymethyl) glycol urea, 1,3-bis(hydroxymethyl) urea, 1,1,3,3-indole (butoxymethyl) Base, urea, 1,1,3,3-indole (methoxymethyl) urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidone, and 1,3- Bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidone and the like. The commercially available product is a compound such as a glycol urea compound (trade name: CYMEL (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Scientech Industries Co., Ltd., Japan. Urea resin (trade name: UFR (registered trademark) 65), methylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (share) (old Urea/formaldehyde resin (high condensation type, trade name: BECKAMINE (registered trademark) J-300S, BECKAMINE P-955, BECKAMINE N) manufactured by Dainippon Ink Chemical Industry Co., Ltd.).

Specific examples of the alkoxymethylated benzoquinone include tetramethoxymethylphenylhydrazine and the like. Commercially available products are manufactured by Japan Scientech Industries Co., Ltd. (trade name: CYMEL (registered trademark) 1123) and Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered trademark) BX- 4000, NIKALAC BX-37, NIKALAC BL-60, NIKALAC BX-55H), etc.

Specific examples of the alkoxymethylated melamine are, for example, hexamethoxymethylmelamine. Commercially available products are, for example, methoxymethyl type melamine compounds manufactured by Scientech Industries, Ltd. (trade name: CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL, manufactured by Scientech Industries, Japan. 350), a methoxymethyl type melamine compound (trade name: MYCOTE (registered trademark) 506, MYCOTE 508), a methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (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 melamine compound (commodity) Name: NIKALAC (registered trademark) MX-45, NIKALAC MX-410, NIKALAC MX-302).

Further, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycol urea compound, and a benzoquinone compound in which a hydrogen atom of these amine groups is substituted with a methylol group or an alkoxymethyl group. For example, a melamine compound described in U.S. Patent No. 6,323,310 and a high molecular weight compound produced from a benzoquinone compound are listed. The commercially available product of the melamine compound is CYMEL (registered trademark) 303, and the like, and the commercial product of the benzoquinone compound is CYMEL (registered trademark) 1123 (the above is manufactured by Scientech Industries, Japan). .

Further, the crosslinking agent of the component (B) may also be used by using N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N- A polymer produced by a acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group (i.e., a methylol group) or an alkoxymethyl group, such as butoxymethylmethacrylamide.

As such a polymer, for example, copolymerization of poly(N-butoxymethyl acrylamide), N-butoxymethyl acrylamide and styrene is exemplified. a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and N-butoxy a copolymer of methacrylamide and benzyl methacrylate with 2-hydroxypropyl methacrylate. The weight average molecular weight (polystyrene conversion value) of the polymers is from 1,000 to 500,000, preferably from 2,000 to 200,000, more preferably from 3,000 to 150,000, still more preferably from 3,000 to 50,000.

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

The content of the crosslinking agent of the component (B) in the cured film formation composition of the present invention is preferably from 1 part by mass to 100 parts by mass, more preferably from 5 parts by mass to 80 parts by mass based on 100 parts by mass of the compound of the component (A). Parts by mass. When the content of the crosslinking agent is too small, the solvent resistance of the cured film obtained by forming the composition from the cured film is lowered, and the vertical alignment property is lowered. On the other hand, when the content is too large, there is a case where the vertical alignment property and the storage stability are lowered.

<(C) component>

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

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

The component (C) is specifically exemplified by a sulfonic acid group-containing compound as the above acid, hydrochloric acid or a salt thereof. Moreover, the above thermal acid generator is only required to be heat treated The compound which generates an acid by thermal decomposition, that is, a compound which thermally decomposes at a temperature of 80 ° C to 250 ° C to generate an acid, is not particularly limited.

Specific examples of the above acid are exemplified by 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-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1- A sulfonic acid group-containing compound such as a sulfonic acid or dodecylbenzenesulfonic acid or a water or a salt thereof.

And the compound which generates an acid by heat is exemplified by, for example, bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, p-nitrobenzyltoluenesulfonate. Acid ester, o-nitrobenzyl tosylate, 1,2,3-phenylene (methanesulfonate), pyridinium p-toluenesulfonate, morpholinium salt of p-toluenesulfonate , p-toluenesulfonate ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester , p-toluenesulfonic acid cyanomethyl ester, p-toluenesulfonic acid 2,2,2-trifluoroethyl ester, p-toluenesulfonic acid 2-hydroxybutyl ester, N-ethyl-p-toluenesulfonamide, And compounds represented by the following formula:

The content of the component (C) in the cured film formation composition of the present invention is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 0.1 part by mass to 15 parts by mass, per 100 parts by mass of the compound of the component (A). It is more preferably 0.5 parts by mass to 10 parts by mass. By setting the content of the component (C) to 0.01 parts by mass or more, sufficient thermosetting property and resistance to dissolution can be imparted. Dosage. However, when it is more than 20 parts by mass, the storage stability of the composition may be lowered.

Solvent

The cured film forming composition of the present invention is mainly used in the form of a solution dissolved in a solvent. The solvent to be used at this time is not particularly limited as long as it can dissolve the component (A), the component (B), and/or the component (C), and other additives described later, as needed, and the type and structure thereof.

Specific examples of the solvent are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, and B. Glycol monoethyl 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-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxyl Ethyl 2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate , cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide And N- methyl-2-pyrrolidone, and the like.

Forming a composition using the cured film of the present invention, in a resin film When a cured film is formed thereon to produce a alignment material, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2-pentanol, isobutyl methyl ketone, diethylene glycol, Propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferred in terms of a solution in which the resin film exhibits resistance.

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

<Other Additives>

Further, the cured film forming composition of the present invention may contain a coating enhancer, a decane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, and the like as long as the effect of the present invention is not impaired. Foaming agents, antioxidants, etc.

<Modulation of a cured film forming composition>

The cured film forming composition of the present invention contains the vertical alignment polymer of the component (A), the crosslinking agent of the component (B), and/or the acid catalyst of the component (C), and if necessary, does not impair the present invention. Within the scope of the effect, it may further comprise a composition of other additives. Therefore, it is usually used in the form of a solution which dissolves the solvent 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]: based on 100 parts by mass of the (A) component, containing 1 part by mass to 100% The cured film of the component (B) and the solvent are formed into a composition.

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

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

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

The ratio of the solid content in the cured film formation composition of the present invention is not particularly limited as long as the components are uniformly dissolved in the monomer, but it is 1% by mass to 60% by mass, preferably 2% by mass to 50% by mass. More preferably, it is 2% by mass to 20% by mass. Here, the solid content means a solvent from which all components of the cured film forming composition are removed.

The method for preparing the cured film forming composition of the present invention is not particularly limited. The preparation method is, for example, a method in which a component (B) and/or a component (C) are mixed in a solution of the component (A) dissolved in a solvent, or a suitable solution is prepared. In the stage, further add other additives and mix as needed.

In the preparation of the cured film forming composition of the present invention, a solution of a vertically aligned polymer obtained by a reaction in a solvent can be used as it is. In this case, for example, the component (B) and/or the component (C) are fed into the solution of the component (A) in the same manner as described above to form a homogeneous solution. At this time, an additional solvent may be additionally added for the purpose of adjusting the concentration. At this time, the solvent used in the formation of the component (A) can be adjusted with the concentration of the cured film forming composition. The solvent used is the same or different.

Further, the solution of the cured film forming composition to be prepared is preferably filtered using a filter having a pore diameter of about 0.2 μm or the like.

<hardened film, alignment material and phase difference material>

Applying a solution of the cured film of the present invention to a composition by a bar coater, spin coating, flow coating, roll coating, slit coating, slit-spinning spin coating, inkjet coating, printing, or the like A substrate (for example, a tantalum/cerium oxide-coated substrate, a tantalum nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, or the like) or a thin film substrate (for example, triacetonitrile) Cellulose (TAC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene film, etc.) A coating film is formed thereon, and then dried by heating with a hot plate or an oven, whereby a cured film can be formed. The cured film can also be used directly as an alignment material.

The conditions of heat drying may be carried out by crosslinking the crosslinking agent by a crosslinking agent as long as the components of the cured film (alignment material) are not dissolved in the polymerizable liquid crystal solution applied thereto, for example, at a temperature of 60 ° C. Appropriately selected heating temperature and heating time in the range of ~200 ° C, time 0.4 minutes to 60 minutes. The heating temperature and heating time are preferably from 70 ° C to 160 ° C, from 0.5 minutes to 10 minutes.

The film thickness of the cured film (orienting 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 or optical and electrical properties of the substrate to be used.

Since the alignment material formed of 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 a vertical alignment property can be applied onto the alignment material, and aligned on the alignment material. . Further, the phase difference material which is in the alignment state is cured by irradiation of ultraviolet rays of 300 to 400 nm, and a phase difference material can be formed as a layer having optical anisotropy. Further, when the substrate on which the alignment material is formed is a film, a retardation film can be used.

Further, by 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 the spacer, and then liquid crystal is injected between the substrates to form a liquid crystal. Aligned liquid crystal display elements.

The cured film forming composition of the present invention can be preferably used in the production of various phase difference materials (phase difference films) or liquid crystal display elements.

[Examples]

The invention is illustrated in more detail in the following examples, but the invention is not limited to the examples.

[abbreviation symbols used in the examples]

The abbreviated symbols used in the following embodiments have the following meanings.

<Polygonal alignment polymer of (A) component and crosslinking agent (polymer) raw material of (B) component>

jER-1001: bisphenol A epoxy resin manufactured by Mitsubishi Chemical Co., Ltd. Molecular weight 900

jER-1055: bisphenol A epoxy resin manufactured by Mitsubishi Chemical Co., Ltd. Molecular weight 1,600

jER-157S70: epoxidized bisphenol A novolac resin made by Mitsubishi Chemical Corporation

ECN-1299: cresol novolac resin made by Asahi Kasei Co., Ltd.

EHPE-3150: 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct of trimethylolpropane manufactured by Daicel Co., Ltd.

LAUA: Lauric acid

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

BMAA: N-butoxymethyl acrylamide

BTEAC: benzyltriethylammonium chloride

AIBN: α,α'-azobisisobutyronitrile

<(B) component: crosslinking agent>

CYM303: hexamethoxymethyl melamine

<(C) component: acid catalyst>

PTSA: p-toluenesulfonic acid ‧ monohydrate

Solvent

PM: propylene glycol monomethyl ether

MIBK: isobutyl methyl ketone

The number of acrylic copolymers obtained according to the following synthesis examples The average molecular weight and the weight average molecular weight are made using Japan Spectrophotometer The GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) was measured by flowing the elution solvent tetrahydrofuran to a column (column temperature: 40 ° C) at a flow rate of 1 mL/min. In addition, the following average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>

JER-1001 50.0 g, LAUA 6.25 g, and BTEAC 0.14 g were dissolved in PM 131.58 g, and reacted at 110 ° C for 16 hours, thereby obtaining a vertical alignment polymer (solid content concentration: 30% by mass) (P1). The epoxy valence of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group which partially reacts LAUA disappeared.

<Synthesis Example 2>

JER-1055 50.0 g, LAUA 3.54 g, and BTEAC 0.079 g were dissolved in PM 125.0 g, and reacted at 110 ° C for 16 hours, thereby obtaining a vertical alignment polymer (solid content concentration: 30% by mass) (P2). The epoxy valence of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group which partially reacts LAUA disappeared.

<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 ° C for 16 hours to obtain a vertical alignment polymer (solid content concentration: 30% by mass) (P3). Measuring institute The epoxy valence of the vertically aligned polymer was confirmed, and it was confirmed that the epoxy group which partially reacts LAUA disappeared.

<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 ° C for 16 hours to obtain a vertically aligned polymer (solid content concentration: 30% by mass) (P4). The epoxy valence of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group which partially reacts LAUA disappeared.

<Synthesis Example 5>

EHPE-3150 50.0 g, LAUA 5.59 g, and BTEAC 0.036 g were dissolved in PM 129.8 g, and reacted at 110 ° C for 16 hours to obtain a vertical alignment polymer (solid content concentration: 30% by mass) (P5). The epoxy valence of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group which partially reacts LAUA disappeared.

<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: 35 mass%) (P6). The obtained acrylic copolymer had an Mn of 4,800 and a Mw of 3,100.

<Synthesis Example 7>

EHPE-3150 50.0 g, 5 CCA 24.4 g, and BTEAC 0.49 g were dissolved in PM 174.7 g, and reacted at 110 ° C for 16 hours, thereby obtaining a vertical alignment polymer (solid content concentration: 30% by mass) (P7). The epoxy valence of the obtained vertically-oriented polymer was measured, and it was confirmed that the epoxy group which partially reacts 5CCA disappears.

<Examples 1 to 7, Comparative Examples 1, 2>

The cured film formation compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were prepared in the compositions shown in Table 1, and the vertical alignment properties were evaluated for each of the examples.

[Evaluation of vertical alignment]

Each of the cured film forming compositions of the examples and the comparative examples was applied onto an alkali-free glass at 2000 rpm for 30 seconds using a spin coater. Similarly, each of the cured film forming compositions of the examples and the comparative examples was applied onto a PET film with a wet film thickness of 4 μm using a bar coater. Subsequently, heat drying was carried out in a heat cycle oven at a temperature of 100 ° C for 60 seconds to form respective cured films on the glass and on the PET film.

Using a bar coater, a vertical alignment of a Merck (manufactured by Merck) was applied to the cured film by a polymerizable liquid crystal solution RMS03-015 at a wet film thickness of 6 μm, and allowed to stand at room temperature at 23 ° C for 60 seconds. The coating film on the substrate was exposed at 300 mJ/cm ² to prepare a phase difference material. Further, the polymerizable liquid crystal solution was directly applied onto a glass and a PET film (the cured film was formed into a cured film by a cured film), and a phase difference material produced in the same order was used as Comparative Example 3.

The incident angle dependence of the in-plane phase difference of the produced phase difference material was measured using a phase difference measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. The in-plane phase difference value at the incident angle of 0 degrees is 0, and the vertical phase is judged when the phase difference of the incident angle of ±50 degrees is 38±5 nm. The results obtained are shown in Table 2.

[Evaluation of liquid crystal coating properties]

Each of the cured film forming compositions of the examples and the comparative examples was applied onto a PET film with a wet film thickness of 4 μm using a bar coater. Subsequently, heat drying was performed in a heat cycle oven at a temperature of 100 ° C for 60 seconds to form a cured film on the PET film.

Using a bar coater, a vertical alignment of a Merck (manufactured by Merck) was applied to the cured film by a polymerizable liquid crystal solution RMS03-015 at a wet film thickness of 6 μm, and left at room temperature for 23 seconds at 23 ° C. The coating film on the substrate was exposed at 300 mJ/cm ² to prepare a phase difference material. Further, the polymerizable liquid crystal solution was directly applied onto a PET film (the cured film was formed into a cured film by a cured film), and a phase difference material produced in the same order was used as Comparative Example 3.

When the phase difference material was visually observed, it was judged that the liquid crystal coating property was good without causing pinholes due to the non-sticking of the liquid crystal.

The results obtained are shown in Table 2.

As shown in Table 2, the cured film obtained by forming the composition of the cured films of Examples 1 to 7 as the phase difference material of the alignment material did not differ depending on the use of the substrate, and both exhibited good vertical alignment, and liquid crystal The coatability is also good.

On the other hand, a cured film obtained by forming a composition of the cured film of Comparative Example 1 containing no one of the crosslinking agent (B) and the acid catalyst (C) is used as a phase difference material of the alignment agent, and The cured film obtained by using the cured film of Comparative Example 2 containing no component (A) of the vertical alignment group as the phase difference material of the alignment material could not obtain vertical alignment.

Further, the phase difference material of Comparative Example 3 obtained without forming a cured film was Vertical alignment is shown on the glass, but vertical alignment is not shown on the PET.

[Industrial availability]

The cured film forming composition of the present invention is useful as a liquid crystal alignment film for forming a liquid crystal display element, or a material for forming an alignment material of an optical anisotropic film provided inside or outside the liquid crystal display element, and is particularly suitable as an IPS- The material of the optical compensation film of LCD.

Claims (7)

A cured film forming composition characterized by comprising (A) a polymer which reacts a carboxyl group of a compound having a carboxyl group and a vertical alignment group with an epoxy group of a polymer having one or more epoxy groups at a side chain or a terminal group. And at least one compound selected from the group consisting of (B) a crosslinking agent having a methylol group or an alkoxymethyl group and (C) an acid catalyst, wherein the vertical alignment group is represented by the following formula (1) Base, (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 a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring. And any hydrogen atom on the above cyclic group may pass through 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, and 1 carbon atom ~3 is substituted by a fluorine-containing alkoxy group or a fluorine atom, Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, Y ⁴ represents a single bond, or represents a benzene ring, a cyclohexane ring or a heterocyclic ring. a divalent cyclic group or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, and any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms and 1 carbon atom a alkoxy group of ~3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ represents a benzene ring, a cyclohexane ring or a heterocyclic ring a divalent cyclic group is selected, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number of 1 to 3 a fluoroalkyl group, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n represents an integer of 0 to 4, When n is 2 or more, Y ⁵ may be the same or different, and 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, and a carbon number of 1 to 18; Alkoxy or fluoroalkoxy group having 1 to 18 carbon atoms, alkylene group of Y ² and Y ³ , and substituent on the cyclic group or alkyl group of Y ⁶ , fluorine-containing alkyl group, alkoxy group And the fluorine-containing alkoxy group may be any of a linear chain, a branched chain or a cyclic group or a combination thereof, and an alkylene group of Y ² and Y ³ , an alkyl group of Y ⁶ , a fluorine-containing alkyl group, The alkoxy group and the fluorine-containing alkoxy group may be interrupted by 1 to 3 bonding groups as long as the bonding groups are not adjacent to each other, and further Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, or Y ⁴ represents a divalent organic group having a steroid skeleton, or Y ² or Y ³ representing an alkylene group, or Y ⁶ representing an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having a steroid skeleton, The alkylene group, the alkyl group and the fluorine-containing alkyl group may also be bonded to the group adjacent to the bonding group, and the above bonding group is represented by -O-, -CH ₂ O-, -CO -, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH-, and -NH-CO-NH- The group of the selected groups, the carbon atoms represented by each of Y ² to Y ⁶ extending alkyl of 1 to 15, a benzene ring, a cyclohexane ring, a heterocyclic ring, a divalent organic group having a steroid skeleton of carbon atoms, The total number of carbon atoms of the alkyl group of 1 to 18, the fluorine-containing alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, and the fluorine-containing alkoxy group having 1 to 18 carbon atoms is 6 ~30). The cured film forming composition of claim 1, wherein the polymer having one or more epoxy groups in the side chain or terminal is a polymer having a number average molecular weight of 300 to 20,000 having a ring structure on the main chain. A cured film forming composition according to claim 1 or 2, wherein the polymer having one or more epoxy groups in the side chain or terminal is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac Type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin and polyol 1,2-epoxy-4-(2-epoxyethyl)cyclohexane addition Any polymer selected from the group consisting of objects. The cured film forming composition according to claim 1 or 2, wherein the component (B) is contained in an amount of from 1 part by mass to 100 parts by mass based on 100 parts by mass of the component (A). The cured film forming composition of claim 1 or 2, wherein the component (C) is contained in an amount of from 0.01 part by mass to 20 parts by mass based on 100 parts by mass of the component (A). An alignment material characterized by hardening a cured film forming composition according to any one of claims 1 to 5. A phase difference material characterized by being formed using a cured film obtained by forming a composition of the cured film according to any one of claims 1 to 5.