JP6700609B2 - Cured film forming composition, aligning material and retardation material - Google Patents

Description

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

  The IPS-LCD is characterized in that the change in brightness/color change depending on the viewing angle is small because the liquid crystal molecules are not tilted in the vertical direction, but it is difficult to increase the contrast ratio, brightness, and response speed. Be done. For example, as disclosed in Patent Document 1, in the IPS-LCD in the early stage of the proposal, a viewing angle compensation film is not used, and in an IPS-LCD that does not use such a viewing angle compensation film, a tilt angle of It has the disadvantage of exhibiting low contrast ratio values due to relatively large light leakage in the dark state.

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 therein has the following configuration.
1) A liquid crystal layer having horizontal alignment is sandwiched between both substrates supplied by electrodes capable of applying an electric field parallel to the liquid crystal layer surface.
2) One or more +A plate and +C plate are sandwiched between both polarizing plates.
3) The main optical axis of the +A plate is perpendicular to the main optical axis of the liquid crystal layer.
4) of the liquid crystal layer retardation value _R LC, + C plate retardation value _{R +} C, + A retardation value _{R + A} plate is determined so as to satisfy the following equation.
R _LC : R _+C : R _+A ≈ 1:0.5:0.25
5) The relationship between the retardation values of the +A plate and the +C plate and the retardation value in the thickness direction of the protective film of the polarizing plate is not shown (TAC, COP, PNB).

  Further, a +A plate for the purpose of providing an IPS-LCD having high contrast characteristics in the front and tilt angles and low color shift (Color Shift) by minimizing light leakage in a dark state at the tilt angle. An IPS-LCD having a +C plate and a +C plate is disclosed (Patent Document 3).

JP-A-2-256023 JP-A-11-133408 JP, 2009-122715, A JP 2001-281669 A

As proposed in the related art, the +C plate is capable of compensating for light leakage in a polarizing plate with a wide viewing angle, and thus is very useful as an optical compensation film for an IPS-LCD. However, it is difficult to develop the vertical alignment (positive C plate) property by the conventionally known method of stretching.
Further, in the conventionally proposed vertical alignment film using polyimide, it is necessary to use a solvent of polyimide such as N-methyl-2-pyrrolidone for forming the film. For this reason, a glass substrate is not a problem, but when the substrate is a film, there is a problem that the substrate is damaged when the alignment film is formed. In addition, the vertical alignment film using polyimide needs to be baked at a high temperature, which causes a problem that the film substrate cannot withstand the high temperature.
Furthermore, 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, but when a hydroxy group does not exist on the substrate surface, There is a problem that the treatment is difficult and the base material is limited (Patent Document 4).

  The present invention has been made based on the above findings and examination results, the problem to be solved is to have excellent vertical alignment properties, transparency and solvent resistance required for the optical compensation film, further, A cured film-forming composition for providing an aligning material that has adhesiveness to a substrate and a polymerizable liquid crystal layer and can stably align a polymerizable liquid crystal vertically even on a resin film under low-temperature and short-time firing conditions. It is to provide things.

  And another object of the present invention is obtained from the above cured film forming composition, which has an excellent vertical alignment property and stably aligns the polymerizable liquid crystal vertically even on a resin film under low temperature and short time baking conditions. An object of the present invention is to provide a useful retarder for an orientable material and a +C plate formed by using the orientable material.

  In order to achieve the above-mentioned object, the present inventors have conducted extensive studies and as a result, by selecting a cured film forming material based on an acrylic copolymer having a long-chain alkyl group in a side chain, The present invention has been completed based on the finding that a cured film having excellent vertical alignment and adhesiveness to a substrate and a polymerizable liquid crystal layer can be formed regardless of the above.

That is, the present invention, as a first aspect,
(A) A polymer obtained by reacting a carboxyl group of a compound having a carboxyl group and a vertically aligning group with an epoxy group of a polymer having one or more epoxy groups on a side chain or a terminal, (B) a crosslinking agent, and ( A cured film-forming composition containing one or both of C) an adhesion promoter and (D) a polymer having a heat-crosslinkable group,
The vertical alignment group is a group represented by the following formula [1], and relates to a cured film forming composition.

(In formula [1],
* Represents the bond position,
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 or a heterocyclic ring, and any hydrogen atom on the cyclic group is a carbon atom. Substituted with an alkyl group having 1 to 3 atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom Well,
Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,
Y ⁴ represents a single bond, a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, or a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton. Any hydrogen atom on the group is 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, or fluorine containing 1 to 3 carbon atoms It may be substituted with an alkoxyl group or a fluorine atom,
Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or 1 to 3 carbon atoms. An alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or may be substituted with a fluorine atom,
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, a C 1-18 alkyl group, a C 1-18 fluorine-containing alkyl group, a C 1-18 alkoxyl group, or a C 1-18 fluorine-containing alkoxyl group. ,
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 are linear, branched, or cyclic. Either or a combination thereof,
Further, the alkylene group as Y ² and Y ³ and the alkyl group, the fluorine-containing alkyl group, the alkoxyl group and the fluorine-containing alkoxy group as Y ⁶ are interrupted by 1 to 3 bonding groups unless the bonding groups are adjacent to each other. May have been
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 a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having the steroid skeleton, the alkylene group, the alkyl group and the fluorine-containing alkyl group are groups adjacent to them. And may be bonded via a bonding group,
And said linking _{group, -O -, - CH 2 O} -, - CO -, - COO -, - OCO -, - NHCO -, - CONH -, - NHCO-O -, - OCO-NH Represents a group selected from the group consisting of
Provided that each of Y ^{2 to} Y ⁶ represents an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocycle, a divalent organic group having a steroid skeleton, 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 alkoxyl group having 1 to 18 carbon atoms, and the fluorine-containing alkoxyl group having 1 to 18 carbon atoms is 6 to 30).

As a second aspect, the cured film formation according to the first aspect, wherein the polymer having one or more epoxy groups on a side chain or terminal is a polymer having a ring structure in the main chain and a number average molecular weight of 300 to 20,000. It relates to a composition.
As a third aspect, the polymer having one or more epoxy groups in the side chain or at the terminal is bisphenol A type epoxy resin, bisphenol F epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin. And a cured film forming composition according to the first or second aspect, which is any one polymer selected from the group consisting of a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of a polyol. ..
As a fourth aspect, the cured film-forming composition according to any one of the first to third aspects, wherein the crosslinking agent as the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
A fifth aspect relates to the cured film-forming composition as described in any one of the first to fourth aspects, which further contains (E) a crosslinking catalyst.
As a sixth aspect, based on 100 parts by mass of the component (A), the cured film formation according to any one of the first to fifth aspects, which contains 1 part by mass to 300 parts by mass of the component (B). It relates to a composition.
As a seventh aspect, 0.1 parts by mass to 100 parts by mass of the component (C) and 1 part by mass to 400 parts by mass based on 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent as the component (B). The cured film-forming composition according to any one of the first to sixth aspects, which contains either one or both of the parts by weight of the component (D).
An eighth aspect relates to the cured film-forming composition as described in any of the fifth aspect to the seventh aspect, which contains 0.01 to 20 parts by mass of the component (E).
A ninth aspect relates to an alignment material, which is obtained by curing the cured film forming composition according to any one of the first to eighth aspects.
A tenth aspect relates to a retardation material, which is formed by using a cured film obtained from the cured film forming composition according to any one of the first to eighth aspects.

  According to the first aspect of the present invention, in order to provide an alignment material having excellent vertical alignment properties and capable of stably aligning a polymerizable liquid crystal vertically even on a resin film under low temperature and short time firing conditions. A useful cured film forming composition can be provided.

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

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

<Cured film forming composition>
The cured film-forming composition of the present invention is obtained by reacting (A) an epoxy group of a polymer having one or more epoxy groups on its side chain or terminal with a carboxyl group of a compound having a carboxyl group and a vertical alignment group. One or both of a polymer, (B) a crosslinking agent, and (C) an adhesion promoter and (D) a polymer having a heat-crosslinkable group are contained. The cured film forming composition of the present invention may further contain a crosslinking catalyst as the component (E) in addition to the components (A), (B), (C) and (D). .. And other additives may be contained as long as the effects of the present invention are not impaired.
The details of each component will be described below.

<(A) component>
The component (A) contained in the cured film-forming composition of the present invention is a carboxyl group of a compound having a carboxyl group and a vertical alignment group with respect to an epoxy group of a polymer having one or more epoxy groups on its side chains or terminals. It is a polymer in which groups are reacted. In the following description, the polymer as the component (A) is also referred to as "vertically oriented polymer".

  The polymer having one or more epoxy groups on the side chain or 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 on the side chain or terminal can be produced by reacting a polymer compound having a hydroxy acid group with a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.

  Specific examples of the polymer having one or more epoxy groups on the side chain or terminal include, for example, 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 novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, trimethylolpropane 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct Etc.

  Among these polymers having one or more epoxy groups on the side chain or terminal, those having a ring structure in the main chain are preferable, and specifically, bisphenol A type epoxy resin, bisphenol F epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of polyol and the like are preferable from the viewpoint of improving the coating property of liquid crystal.

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

  Commercially available polymers having at least one epoxy group on the side chain or at the terminal can be preferably used. Specific examples of the bisphenol A type epoxy resin include jER1001, 1002, 1003, 1004, and jER1001. 1055, 1007, 1009, 1010, 834, 828 (manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be used as bisphenol F-type epoxy resins by jER806, 807 (manufactured by Mitsubishi Chemical Co., Ltd.). ), etc., as the phenol novolac type epoxy resin, jER152, 154 (above, manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.) and the like, cresol novolac type epoxy resin Examples include ECN-1299 (manufactured by Asahi Kasei Corp.), EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.), jER80S75. (Manufactured by Mitsubishi Chemical Co., Ltd.) and the like, as bisphenol A novolac type epoxy resin, jER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.) and the like are 1,2-epoxy-4-(2-oxyranyl)cyclohexane adducts of polyol. Examples include EHPE-3150 (manufactured by Daicel Corp.) and the like.

In the present specification, the vertical orientation group represents, for example, a group containing a hydrocarbon group having about 6 to 20 carbon atoms, and specifically refers to a group represented by the formula [1] described later.
Therefore, examples of the compound having a carboxyl group and a vertical orientation group include a compound having a carboxyl group and a hydrocarbon group having about 6 to 20 carbon atoms.
Examples of the hydrocarbon group having 6 to 20 carbon atoms include linear, branched or cyclic alkyl groups having 6 to 20 carbon atoms or hydrocarbon groups having 6 to 20 carbon atoms including an aromatic group. ..

（式中、＊は結合位置を表す。）More specifically, the vertical alignment group is a group represented by the following formula [1].

(In the formula, * represents a bonding position.)

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

In formula [1], Y ² represents an alkylene group having 1 to 15 carbon atoms.
Examples of Y ² include a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or 1 carbon atom. May be substituted with an alkoxyl group having 3 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.

  As the heterocycle, 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, a carbazole ring, a purine ring, a thiadiazole ring, a pyridazine ring, a pyrazoline ring, Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring and the like, more preferable. Is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, and a benzimidazole ring.

  Examples of the alkyl group mentioned as the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group, and examples of the alkoxyl group include oxygen as a group mentioned as a specific example of the alkyl group. A group in which an atom —O— is bonded can be mentioned. Examples of the above-mentioned fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the above-mentioned alkyl group and alkoxyl group is substituted with a fluorine atom.

Among these, Y ² is preferably a benzene ring or a cyclohexane ring from the viewpoint of ease of synthesis.

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

In the above formula [1], Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups has 1 carbon atom(s). May be substituted with an alkyl group having 3 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.

The heterocyclic ring and the alkyl group and the like mentioned as the substituents may be the same as those mentioned above for Y ² .

Further, Y ⁴ may be a divalent organic group having 17 to 30 carbon atoms and selected from organic groups having a steroid skeleton. Preferred examples thereof are cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, ergosteryl, estryl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, melatranil, methyltestosterolyl, norethisteryl, pregnenonyl, β-sitosteryl, It is a divalent group having a structure in which two hydrogen atoms have been removed from a structure selected from stigmasteryl, testosteryl, acetic acid cholesterol ester and the like. More specifically, for example, it is as follows.

(In the formula, * represents a bonding position with Y ³ and Y ⁵ (or Y ⁶ ).)
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 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 represents an alkyl group having 1 to 3 carbon atoms, It may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. The heterocyclic ring and the alkyl group and the like mentioned as the substituents may be the same as those mentioned above for Y ⁴ .

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

Further, in the formula [1], n represents an integer of 0 to 4, and when n is 2 or more, Y ^{5 s} may be the same group or different groups. Among them, n is preferably 0 to 3 from the viewpoint of availability of raw materials and ease of synthesis. More preferably, it is 0-2.

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

Among them, Y ⁶ is 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. Preferably. More preferably, Y ⁶ is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferably, Y ⁶ is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

In addition, when Y ⁴ is a divalent organic group having a steroid skeleton, Y ⁶ is preferably a hydrogen atom.

  The alkylene group, alkyl group, fluorine-containing alkyl group, alkoxyl group or fluorine-containing alkoxy group mentioned in the definition in the above formula [1] may be linear, branched, or cyclic, or a combination thereof. Good.

  For example, the alkyl group is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n. -Butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl- n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2 ,3-Dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group Group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl- n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl -N-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2- Ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl- n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n -Heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2- Dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl -N-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl 2-ethyl-3-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group Group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group and the like.

Examples of the alkylene group include a divalent group obtained by removing one arbitrary hydrogen atom from the alkyl group.
Examples of the alkoxyl group include groups in which an oxygen atom —O— is bonded to the group described as a specific example of the alkyl group.
Examples of the above-mentioned fluorine-containing alkyl group and fluorine-containing alkoxyl group include groups in which any hydrogen atom of the above-mentioned alkyl group and 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 are linear, branched or cyclic. Or any combination thereof.

The alkylene group as Y ² and Y ³ , and the alkyl group, the fluorine-containing alkyl group, the alkoxyl group and the fluorine-containing alkoxy group as Y ⁶ are 1 to 3 bonding groups unless the bonding groups are adjacent to each other. It may be suspended.

Furthermore, 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 ^{When 6} represents an alkyl group or a fluorine-containing alkyl group, the divalent cyclic group, the divalent organic group having the steroid skeleton, the alkylene group, the alkyl group and the fluorine-containing alkyl group are adjacent to them. It may be bonded to the group via a bonding group.

The above linking _{group, -O -, - CH 2 O} -, - CO -, - COO -, - OCO -, - NHCO -, - CONH -, - NHCO-O -, - OCO-NH -And -NH-CO-NH- represents a group selected from the group consisting of.

In addition, an alkylene group having 1 to 15 carbon atoms, a benzene ring, a cyclohexane ring, a heterocycle, a divalent organic group having a steroid skeleton, and an alkyl group having 1 to 18 carbon atoms, each of which is represented by Y ^{2 to} Y ^6. , The total number of carbon atoms of the fluorine-containing alkyl group having 1 to 18 carbon atoms, the alkoxyl group having 1 to 18 carbon atoms, and the fluorine-containing alkoxyl group having 1 to 18 carbon atoms is 6 to 30, and for example, 6 to Twenty.
Among these, the vertical alignment 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 coating property of the polymerizable liquid crystal.

  Examples of the preferred vertically-oriented group include a hydrocarbon group having about 6 to 20 carbon atoms. Examples of the hydrocarbon group having 6 to 20 carbon atoms include a linear, branched or cyclic hydrocarbon group having 6 to 20 carbon atoms including an alkyl group or aromatic group having 6 to 20 carbon atoms. ..

As the vertical alignment group, for example, Y ^{1 to} Y ⁴ are single bonds, Y ³ is a single bond or an alkylene group having 1 to 15 carbon atoms, n is 0, and Y ⁶ is a carbon atom. The group which is an alkyl group of the number 1-18 is mentioned, Especially, the group represented by Formula [1] is a vertical orientation group (a-1) which is an alkyl group whose total number of carbon atoms is 6-20. Is preferred. Specific examples of such an alkyl group include, among the above-mentioned alkyl groups, an alkyl group having a total of 6 to 20 carbon atoms.

（式中、Ｙ^６は炭素原子数１〜１８のアルキル基である。また＊は結合位置を表す。）In addition to the above, Y ^{1 to} Y ⁴ are, for example, a single bond, n is 2 to 3, and Y ⁵ is a group selected from a benzene ring and a cyclohexane ring. ^The vertical aligning group (a-2) in which ⁶ is an alkyl group having 1 to 18 carbon atoms is preferable. As such a group (a-2), the following (a-2-1) to (a-2-6) are preferable.

(In the formula, Y ⁶ is an alkyl group having 1 to 18 carbon atoms. * represents a bonding position.)

（式中、＊は結合位置を表す。）In addition to the above, as the vertical alignment group, for example, Y ^{1 to} Y ³ are single bonds, Y ⁴ is a steroid skeleton, n is 0, and Y ⁶ is a hydrogen atom. The group (a-3) is preferred. Examples of such a group (a-3) include vertical alignment groups (a-3-1) to (a-3-8) represented by the following formula.

(In the formula, * represents a bonding position.)

  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 vertical alignment group.

The vertically aligned polymer as the component (A) in the present invention is obtained by reacting a carboxyl group and a carboxyl group of a compound having a vertically aligned group with an epoxy group of a polymer having one or more of the above-mentioned epoxy groups in its side chain or terminal. Polymer. By the reaction of the epoxy group and the carboxyl group, a bond of —CH ₂ —CH(OH)—CH ₂ — is generated.

  The amount of the polymer having one or more epoxy groups in the side chain or terminal and the compound having the carboxyl group and the vertically aligning group for obtaining the above vertically aligned polymer is 1 or more in the side chain or terminal. It is preferable to use the compound having a carboxyl group and a vertical alignment group in an amount of 5 to 60 equivalents relative to 1 equivalent of epoxy in the polymer.

  When the carboxyl group of the compound having a carboxyl group and a vertical alignment group is less than 5 equivalents to 1 equivalent of epoxy of a polymer having one or more epoxy groups in the side chain or terminal, the desired vertical alignment polymer is obtained. In some cases, vertical alignment may not be sufficiently obtained. Further, when the carboxyl group of the compound having a carboxyl group and a vertical alignment group exceeds 60 equivalents, a cured film (alignment material) is formed using the vertical alignment polymer, and a polymerizable liquid crystal solution or the like is applied onto it. At this time, the coating property of the liquid crystal may be lowered (repelling of the liquid crystal may occur).

  Further, an epoxy residue of a polymer which does not contain a vertically aligning group and has a carboxyl group-containing compound reacted with a compound having a carboxyl group and a vertically aligning group and having one or more epoxy groups at the side chains or terminals. May be reacted with. In that case, the amount of the carboxyl group per 1 equivalent of epoxy of the polymer having one or more epoxy groups in the side chain or terminal does not include the carboxyl group of the compound having the carboxyl group and the vertical alignment group and the vertical alignment group. The total amount of carboxyl groups in the compound having a carboxyl group is preferably 5 to 60 equivalents.

  The procedure for obtaining the vertically aligned polymer used in the present invention is not particularly limited. For example, a polymer having one or more epoxy groups at the side chains or terminals, a compound having a carboxyl group and a vertically aligned group, and optionally a vertically aligned group may be used. It can be obtained by reacting a compound having no carboxyl group and having a carboxyl group in a solvent in which a reaction catalyst and the like coexist at a temperature of 50 to 150°C. At that time, the solvent used is not particularly limited as long as it dissolves the polymer having one or more epoxy groups in the side chain or terminal, the compound having the carboxyl group and the vertical alignment group, the reaction catalyst and the like. As specific examples thereof, those listed below in <solvent> can be preferably used. As the reaction catalyst, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride , Quaternary ammonium salts such as tetrapropylammonium bromide; quaternary phosphones such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide Examples of such salts include a aluminum salt.

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

Further, the solution of the vertically aligned polymer obtained by the above method is put into diethyl ether or water under stirring to reprecipitate, and the generated precipitate is filtered and washed, and then at normal pressure or reduced pressure at room temperature. The powder of the vertically aligned polymer can be obtained by drying or heat drying. By the above operation, the reaction catalyst and the unreacted compound that coexist with the vertically aligned polymer can be removed, and as a result, a purified vertically aligned polymer powder can be obtained. If the powder cannot 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 aligned polymer may be used in the form of powder or in the form of a solution in which purified powder is redissolved in a solvent described later.

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

<(B) component>
The component (B) in the cured film forming composition of the present invention is a crosslinking agent.
The cross-linking agent which is the component (B) is preferably a cross-linking agent having a group that forms a cross-link with the thermally crosslinkable functional group of the component (A), for example, a methylol group or an alkoxymethyl group.
Examples of compounds having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine and alkoxymethylated melamine.

  Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4. ,6-Tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) Urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone and the like can be mentioned. As commercially available products, compounds such as glycoluril compound (trade name: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.), methylated urea resin (Brand name: UFR (registered trademark) 65), butylated urea resin (Brand name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (former Dainippon Ink and Chemicals) Urea/formaldehyde resin (high condensation type, trade name: Beckamine (registered trademark) J-300S, P-955, N) manufactured by Kogyo Co., Ltd. and the like can be mentioned.

  Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethyl benzoguanamine and the like. As commercially available products, manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade name: Nikalac (registered trademark) BX- 4000, BX-37, BL-60, BX-55H) and the like.

  Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like. As commercially available products, Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine Compounds (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) MW-30, MW-22, MW-) 11, the same MS-001, the same MX-002, the same MX-730, the same MX-750, the same MX-035), a butoxymethyl type melamine compound (trade name: Nicalac (registered trademark) MX-45, the same MX-410). , MX-302) and the like.

  In addition, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group. Examples include high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310. Commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 and the like, and commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (above, Nippon Cytec Industries (Japan) Co., Ltd. ) (Formerly manufactured by Mitsui Cytec Co., Ltd.) and the like.

  Furthermore, as a cross-linking agent of the component (B), a hydroxymethyl group (that is, a methylol group) or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. Polymers produced using acrylamide compounds or methacrylamide compounds substituted with can also be used.

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

  These crosslinking agents can be used alone or in combination of two or more kinds. Further, a polymer having an N-alkoxymethyl group as a unit structure and a polymerizable group containing a C═C double bond, which is also exemplified as the component (C) described below, also as a crosslinking agent of the component (B) (specification It is also possible to use the copolymer 2).

The content of the crosslinking agent as the component (B) in the cured film-forming composition of the present invention is preferably 1 part by mass to 300 parts by mass, more preferably 100 parts by mass of the polymer as the component (A). It is 5 to 200 parts by mass. When the content of the cross-linking agent is too small, the solvent resistance of the cured film obtained from the cured film-forming composition is lowered and the vertical alignment property is lowered. On the other hand, if the content is too large, the vertical alignment property and storage stability may decrease.

<(C) component>
The cured film forming composition of the present invention contains either or both of a component (C): an adhesion promoter and a component (D) described below: a polymer having a heat-crosslinkable group.
The component (C) of the present invention is a component (hereinafter, also referred to as an adhesion improving component) that improves the adhesiveness of the cured film to be formed.
As will be described later, when the specific copolymer 2 is used as the component (B), the component (C) may be the same as the component (B).

  When a cured film formed from the cured film-forming composition of the present embodiment containing the component (C) is used as an aligning material, a polymerizable liquid crystal is used to improve the adhesion between the aligning material and the polymerizable liquid crystal layer. The polymerizable functional group and the crosslinking reaction site of the alignment material can be linked by a covalent bond. As a result, the retardation material of the present embodiment, which is obtained by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment, can maintain strong adhesion even under the condition of high temperature and high humidity, such as peeling. It can exhibit high durability against.

As the component (C), a monomer or polymer having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group is preferable.
Examples of the component (C) include compounds having a hydroxy group and a (meth)acryl group, compounds having an N-alkoxymethyl group and a (meth)acryl group, and N-alkoxymethyl groups and a (meth)acryl group. And the like. Specific examples are shown below.

As an example of the component (C), a polyfunctional acrylate containing a hydroxy group (hereinafter, also referred to as a hydroxy group-containing polyfunctional acrylate) can be mentioned.
Examples of the hydroxy group-containing polyfunctional acrylate which is an example of the component (C) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

（上記式中、Ｒ^１１は水素原子またはメチル基を表し、ｍは１〜１０の整数を表す。）Examples of the component (C) also include compounds having one acrylic group and one or more hydroxy groups. Preferred examples of such a compound having one acrylic group and one or more hydroxy groups will be given. The compound as the component (C) is not limited to the following compound examples.

(In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.)

  Examples of the compound as the component (C) include compounds having at least one polymerizable group containing a C=C double bond and at least one N-alkoxymethyl group in one molecule.

  Examples of the polymerizable group containing a C=C double bond include an acrylic group, a methacrylic group, a vinyl group, an allyl group, and a maleimide group.

  N of the N-alkoxymethyl group, that is, the nitrogen atom, is adjacent to an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, and a nitrogen-containing heterocycle nitrogen atom. And a nitrogen atom bonded to. Therefore, as the N-alkoxymethyl group, a nitrogen atom bonded to an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, or a nitrogen atom in a nitrogen-containing heterocycle is adjacent to the nitrogen atom. Examples thereof include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.

（式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２は水素原子、若しくは直鎖又は分岐の炭素原子数１乃至１０のアルキル基を表す）The component (C) may be any one having the above groups, but preferably, for example, a compound represented by the following formula (X1) can be mentioned.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.)

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group. Group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group , 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n- Pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl -N-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1, 2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n- Heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group Group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl- n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1 -Ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group Group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n- Hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n -Hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n -Pentyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n- A decyl group and the like can be mentioned.

  Specific examples of the compound represented by the above formula (X1) include N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth). Examples thereof include acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group such as acrylamide. Note that (meth)acrylamide means both methacrylamide and acrylamide.

  As another aspect of the compound having a C=C double bond-containing polymerizable group and the N-alkoxymethyl group of the component (C), a compound represented by the following formula (X2) is preferably exemplified. ..

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵² and R ⁵³ are each independently a linear or branched alkylene group having 2 to 20 carbon atoms, an aliphatic ring group having 5 to 6 carbon atoms, or a fat containing an aliphatic ring having 5 to 6 carbon atoms. It represents a group group and may have an ether bond in the structure. R ⁵⁴ represents a linear or branched alkyl group having 1 to 20 carbon atoms, an aliphatic ring group having 5 to 6 carbon atoms, or an aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, One methylene group or a plurality of methylene groups which are not adjacent to each other may be replaced with an ether bond. Z is >NCOO-, or -OCON< (where "-" indicates that there is one bond. Also, ">" and "<" indicate that there are two bonds, and It means that an alkoxymethyl group is bonded to either one of the bonds.). r is a natural number of 2 or more and 9 or less.

Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of R ⁵³ and R ⁵⁴ include divalent to 9 valent groups obtained by further removing 1 to 8 hydrogen atoms from an alkyl group having 2 to 20 carbon atoms. Groups.

  Specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n. -Pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, n-hexyl group, 1-methyl -N-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, n- Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n- Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, a group in which one or more of them are bonded in a range of up to 20 carbon atoms, and one of these groups An example is methylene or a group in which a plurality of methylene groups that are not adjacent to each other are replaced with ether bonds.

Among these, an alkylene group having 2 to 10 carbon atoms is preferable, R ⁵³ is an ethylene group, and R ⁵⁴ is a hexylene group is particularly preferable from the viewpoint of availability of raw materials and the like.

Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of R ⁵² include specific examples of the alkyl group having 2 to 20 carbon atoms in the definition of R ⁵³ and R ⁵⁴ , and a methyl group. Of these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferable.

  Examples of r include natural numbers of 2 or more and 9 or less, and among them, 2 to 6 are preferable.

Compound (X2) is obtained by the production method represented by the following reaction scheme. That is, a carbamate compound having an acryl or methacryl group represented by the following formula (X2-1) (hereinafter, also referred to as compound (X2-1)) is treated with trimethylsilyl chloride and paraformaldehyde (generally represented by the chemical formula (CH ₂ O)n. And an alcohol represented by R ⁵² —OH is added to the reaction solution to react. Manufactured by.

In the formula, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , Z and r represent the above meanings, and X represents —NHCOO— or —OCONH—.

  The amounts of trimethylsilyl chloride and paraformaldehyde used with respect to compound (X2-1) are not particularly limited, but in order to complete the reaction, trimethylsilyl chloride is 1.0 to 6.0 equivalent times with respect to one carbamate bond in the molecule, Paraformaldehyde is preferably used in an amount of 1.0 to 3.0 equivalents, and the equivalent of trimethylsilyl chloride used is more preferably greater than the equivalent of paraformaldehyde used.

  The reaction solvent is not particularly limited as long as it is inert to the reaction, for example, hydrocarbons such as hexane, cyclohexane, benzene, toluene; methylene chloride, carbon tetrachloride, chloroform, 1,2-dichloroethane, etc. Halogenated hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran; nitriles such as acetonitrile and propionitrile; N,N-dimethylformamide, N,N-dimethylacetamide, N -Nitrogen-containing aprotic polar solvents such as -methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; pyridines such as pyridine and picoline. These solvents may be used alone or in combination of two or more. Preferred are methylene chloride and chloroform, and more preferred is methylene chloride.

  The amount of the above-mentioned solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent, and when a solvent is used, it is 0.1 to 100 relative to the compound (X2-1). You may use the solvent of mass times. The amount is preferably 1 to 30 times by mass, more preferably 2 to 20 times by mass.

  The reaction temperature is not particularly limited, but is, for example, −90 to 200° C., preferably −20 to 100° C., and more preferably −10 to 50° C.

  The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

  The reaction can be carried out under normal pressure or under pressure, and may be a batch system or a continuous system.

  A polymerization inhibitor may be added during the reaction. As such a polymerization inhibitor, BHT (2,6-di-tert-butyl-para-cresol), hydroquinone, para-methoxyphenol or the like can be used, and it inhibits the polymerization of acrylic group and methacrylic group. If there is no particular limitation.

  The addition amount of the polymerization inhibitor is not particularly limited, but is 0.0001 to 10 wt %, preferably 0.01 to 1 wt% with respect to the total amount (mass) of the compound (X2-1) used. is there. In this specification, wt% means mass %.

  In the step of reacting the intermediate (X2-2) with alcohol, a base may be added in order to suppress hydrolysis under acidic conditions. Examples of the base include pyridines such as pyridine and picoline, and tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and tributylamine. Preferred are triethylamine and diisopropylethylamine, and more preferred is triethylamine. The addition amount of the base is not particularly limited, but may be 0.01 to 2.0 equivalent times, more preferably 0.5 to 1 equivalent to the addition amount of trimethylsilyl chloride used in the reaction. 0.0 equivalent.

  Moreover, after obtaining the intermediate (X2-2) from the compound (X2-1), alcohol may be added and reacted without isolating the intermediate (X2-2).

  The synthesis method of the compound (X2-1) is not particularly limited, but it is produced by reacting a (meth)acryloyloxyalkyl isocyanate with a polyol compound or by reacting a hydroxyalkyl (meth)acrylate compound with a polyisocyanate compound. You can do it.

  Specific examples of the (meth)acryloyloxyalkyl isocyanate include 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz MOI [registered trademark]), 2-acryloyloxyethyl isocyanate (Showa Denko). The product name is Karens AOI [registered trademark] manufactured by Denko KK and the like.

  Specific examples of the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, Examples thereof include diol compounds such as 1,6-hexanediol and 1,4-cyclohexanedimethanol, triol compounds such as glycerin and trimethylolpropane, pentaerythritol, dipentaerythritol, and diglycerin.

  Specific examples of the hydroxyalkyl (meth)acrylate compound include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and diethylene glycol. Examples thereof include monomers having a hydroxy group such as monoacrylate, diethylene glycol monomethacrylate, poly(ethylene glycol)ethyl ether acrylate, and poly(ethylene glycol)ethyl ether methacrylate.

  Specific examples of the polyisocyanate compound include hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω. Alicyclic diisocyanate such as'-diisocyanate dimethylcyclohexane, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, Examples thereof include triisocyanate such as bicycloheptane triisocyanate.

  These (meth)acryloyloxyalkyl isocyanate compounds, polyol compounds, hydroxyalkyl (meth)acrylate compounds and polyisocyanate compounds are generally commercially available and can be synthesized by known methods.

In addition, as an example of the component (C), a polymer having an N-alkoxymethyl group and a polymerizable group containing a C=C double bond as a unit structure (hereinafter, also referred to as a specific copolymer 2) is also exemplified. This can also serve as the crosslinking agent of the component (B) as described above, that is, in this case, the component (C) may be the same as the component (B).
..
The specific copolymer is a polymer containing a repeating unit structure containing both groups of an N-alkoxymethyl group and a polymerizable group containing a C=C double bond, or a repeating unit structure containing an N-alkoxymethyl group, A polymer containing a repeating unit containing a polymerizable group containing a C═C double bond, and a repeating unit containing both an N-alkoxymethyl group and a polymerizable group containing a C═C double bond. It may be a polymer containing a unit structure and at least one repeating unit structure of a repeating unit structure containing an N-alkoxymethyl group and a repeating unit containing a polymerizable group containing a C=C double bond. Among these, as the specific copolymer 2, a polymer having a repeating unit structure containing an N-alkoxymethyl group and a repeating unit containing a polymerizable group containing a C═C double bond can be preferably used.
The specific copolymer 2 (also referred to as a polymer of the component (C)), which is an example of the component (C), will be described below.

  N of the N-alkoxymethyl group, that is, the nitrogen atom, is adjacent to an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, and a nitrogen-containing heterocycle nitrogen atom. And a nitrogen atom bonded to. Therefore, as the N-alkoxymethyl group, a nitrogen atom bonded to an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, or a nitrogen atom in a nitrogen-containing heterocycle is adjacent to the nitrogen atom. Examples thereof include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.

The N-alkoxymethyl group-providing monomer (hereinafter, also referred to as a specific monomer X1) may be one having the above group, but is preferably, for example, a compound represented by the above formula (X1) (in the formula: In which R ² represents a linear or branched alkyl group having 1 to 10 carbon atoms).

  Examples of the polymerizable group containing a C=C double bond include an acrylic group, a methacrylic group, a vinyl group, an allyl group, and a maleimide group.

The polymerizable group containing a C=C double bond can be incorporated into a side chain of the main skeleton of the polymer, that is, as the specific side chain having a polymerizable group containing a C=C double bond, the component (C) Can be incorporated into the side chain of the polymer.
The specific side chain having a polymerizable group containing a C=C double bond of the component (C) preferably has 3 to 16 carbon atoms and an unsaturated bond at the terminal, and has the following formula: The specific side chain represented by (b2) is particularly preferable. The specific side chain represented by the formula (b2) is, for example, as shown in the formula (b2-1), bonded to the ester bond portion of the acrylic polymer.

In formula (b2), R ⁴¹ has 1 to 14 carbon atoms, and is an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or from this group An organic group composed of a combination of a plurality of selected organic groups. R ⁴¹ may contain an ester bond, an ether bond, an amide bond, a urethane bond, or the like.

In the specific side chain represented by the formula (b2), R ⁴² is a hydrogen atom or a methyl group, and the specific side chain in which R ⁴² is a hydrogen atom is particularly preferable. More preferably, it is a specific side chain having an acryloyl group, a methacryloyl group or a vinylphenyl group at the end.

In formula (b2-1), R ⁴³ is a hydrogen atom or a methyl group.

The method for obtaining the polymer having the specific side chain as described above is not particularly limited.
As an example, an acrylic polymer having a specific functional group described below (hereinafter, also referred to as a polymer having a specific functional group) is generated by a polymerization method such as radical polymerization in advance. The N-alkoxymethyl group has already been introduced into the polymer as described later). Then, by reacting this specific functional group with a compound having an unsaturated bond (C=C double bond) at the end (hereinafter referred to as a specific compound) to generate a specific side chain, C= A polymer as the component (C) can be obtained by introducing a polymerizable group containing a C double bond.

  Here, the specific functional group refers to a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of kinds of functional groups selected from these. ..

  In the above-mentioned reaction for forming a specific side chain, a preferable combination of a specific functional group and a functional group of a specific compound (for forming a characteristic side chain) involved in the reaction is a carboxyl group and an epoxy group, A hydroxy group and an isocyanate group, a phenolic hydroxy group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride. Furthermore, a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxy group and isocyanate ethyl methacrylate.

  Further, the polymer having a specific functional group used in the reaction for forming the specific side chain described above is preferably a polymer having an N-alkoxymethyl group and a specific functional group. That is, preferably, the polymer having the specific functional group is a specific monomer X1 that is a monomer that gives an N-alkoxymethyl group, and a specific compound that is a compound having an unsaturated bond (C=C double bond) at the terminal. A monomer having a functional group (specific functional group) for reacting, that is, a monomer having a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group (hereinafter, referred to as a specific monomer X3 It is also preferable that the number average molecular weight thereof is 2,000 to 25,000. Here, the monomer having a specific functional group used for the polymerization may be used alone, or a plurality of types may be used in combination as long as they do not react during the polymerization.

  Hereinafter, specific examples of the monomer necessary for obtaining the polymer having the specific functional group, that is, the specific monomer X3 will be given. However, it is not limited to these.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl. ) Maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide and the like.

  Examples of the glycidyl group-containing monomer include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene and 1,7. -Octadiene monoepoxide and the like.

  Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and 2,3-. Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and the like can be mentioned.

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

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

  Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate and m-tetramethylxylene isocyanate.

As described above, in the specific side chain represented by the formula (b2) obtained by the reaction with the specific functional group, specific examples of R ⁴¹ include the following formulas (B-1) to (B-11). ) And the like.

（式中、＊はＲ^４２が結合する二重結合を形成する炭素原子との結合個所を表す。）

(In the formula, * represents a bonding position with a carbon atom forming a double bond to which R ⁴² is bonded.)

  Further, in the present invention, when the polymer of the component (C) is obtained, it can be copolymerized with the specific monomer X1 and the specific monomer X3, and can be thermally crosslinked with the component (A). A monomer having no functional group (that is, a hydroxy group, a carboxyl group, an amino group, an alkoxysilyl group, etc.) can be used in combination.

  Specific examples of such a monomer include an acrylic acid ester compound or a methacrylic acid ester compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, and a styrene compound having a structure different from that of the specific monomer X1 and the specific monomer X3. And vinyl compounds (hereinafter, also referred to as monomer X4).

Hereinafter, specific examples of the monomer X4 will be shown, but the monomer X4 is not limited thereto.
Examples of the acrylic ester compound which is an example of the monomer X4 include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, naphthyl acrylate, and anion. Tolyl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate. , Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tri. Cyclodecyl acrylate etc. are mentioned.

  Examples of the methacrylic acid ester compound that is an example of the monomer X4 include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and amine. Tolyl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate. , Tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8- Ethyl-8-tricyclodecyl methacrylate and the like can be mentioned.

  Examples of the vinyl compound as an example of the monomer X4 include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2. -Epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.

  Examples of the styrene compound that is an example of the monomer X4 include styrene, methylstyrene, chlorostyrene, and bromostyrene.

  Examples of the maleimide compound that is an example of the monomer X4 include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  In the polymer of the component (C), the N-alkoxymethyl group content is preferably 40 mol% to 90 mol%, more preferably 50 mol% to 85 mol%, per 100 mol of all repeating units of the polymer. preferable.

That is, the amount of the specific monomer X1 (monomer giving an N-alkoxymethyl group) used for obtaining the specific copolymer 2 as the component (C) is the same as that of the specific copolymer 2 as the component (C). It is preferably from 40 mol% to 90 mol%, more preferably from 50 mol% to 85 mol%, based on the total amount of all the monomers used for that purpose.
When the total amount is less than 40 mol%, curing by thermal crosslinking with the component (A) may be insufficient, and when it is more than 90 mol%, the adhesion to the liquid crystal layer may be adversely affected. There is.

  In the polymer of the component (C), the proportion of the polymerizable group containing a C═C double bond is preferably 10 mol% to 60 mol %, and 15 mol% per 100 mol of all repeating units of the polymer. More preferably, it is ˜50 mol %.

That is, a functional group for reacting with a specific monomer X3 (a specific compound that is a compound having an unsaturated bond (C=C double bond) at the end) used to obtain the specific copolymer 2 that is the component (C) The amount of the (monomer having a specific functional group) used may be 10 mol% to 60 mol% based on the total amount of all the monomers used for obtaining the specific copolymer 2 which is the component (C). It is more preferably 15 mol% to 50 mol %.
If the total amount is less than 10 mol%, the adhesion to the liquid crystal layer may be insufficient, and if it is more than 60 mol%, the curing by thermal crosslinking with the component (A) may be insufficient. May be.

  The method for obtaining the specific copolymer 2 which is an example of the component (C) is not particularly limited, but, for example, the specific monomer X1, the specific monomer X3, and optionally a monomer (for example, the monomer X4) and a polymerization initiator, etc. It can be obtained by a polymerization reaction in a solvent in which is coexistent at a temperature of 50°C to 110°C. At that time, the solvent to be used is not particularly limited as long as it can dissolve the specific monomer X1, the specific monomer X3, other optional monomers, a polymerization initiator and the like. Specific examples are described in the section [solvent] described later.

  The acrylic polymer, which is an example of the component (C) obtained by the above method, is usually in the state of a solution dissolved in a solvent, and can be used as it is as a solution of the component (C) in the present invention.

  Further, a solution of the acrylic polymer, which is an example of the component (C) obtained by the above method, is reprecipitated by adding it to stirring diethyl ether, water or the like, and after filtering and washing the generated precipitate, The powder of the specific copolymer 2 as the component (C) can be obtained by drying at room temperature or by heating under normal pressure or reduced pressure. By the above operation, the polymerization initiator and the unreacted monomer that coexist with the specific copolymer 2 of the component (C) can be removed, and as a result, the specific copolymer which is an example of the purified component (C). A powder of 2 is obtained. If the powder cannot be sufficiently purified by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  In the composition for forming a cured film on the surface of the optical film of the present invention, the specific copolymer 2 as the component (C) is used in a powder form or in a solution form in which purified powder is redissolved in a solvent described later. May be.

  Further, in the composition for forming a cured film on the surface of the optical film of the present invention, the specific copolymer 2 as the component (C) may be a mixture of plural kinds.

  The weight average molecular weight of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and further preferably 3 1,000 to 50,000.

The content of the component (C) in the cured film-forming composition of the embodiment of the present invention is preferably 0 based on 100 parts by mass of the total amount of the polymer which is the component (A) and the crosslinking agent of the component (B). 0.1 parts by mass to 100 parts by mass, more preferably 5 parts by mass to 70 parts by mass. When the content of the component (C) is 0.1 part by mass or more, sufficient adhesion can be imparted to the formed cured film. However, when the amount is more than 100 parts by mass, the liquid crystal alignment tends to be deteriorated.
When the component (B) is the specific copolymer 2 and the component (C) and the component (B) are the same (the same compound), the blending amount of the component (C) is the blending amount of the component (B). It is assumed as the amount (in this case, the compounding amount of the component (C) is regarded as 0 in terms of compounding).

  Further, in the cured film forming composition of the present embodiment, the component (C) may be a mixture of a plurality of types of compounds of the component (C).

<(D) component>
The cured film-forming composition of the present invention contains one or both of the above-mentioned component (C): adhesion promoter and component (D): polymer having a heat-crosslinkable group.
Examples of the polymer (hereinafter, also referred to as a specific polymer) which is the component (D) of the present invention include an acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, Polymers having a linear or branched structure such as polycarbonate polyols, polycaprolactone polyols, polyalkyleneimines, polyallylamine, celluloses (cellulose or derivatives thereof), phenol novolac resins, melamine formaldehyde resins, cyclic polymers such as cyclodextrins Is mentioned.

  The specific polymer as the component (D) is preferably an acrylic polymer, hydroxyalkyl cyclodextrin, cellulose, polyether polyol, polyester polyol, polycarbonate polyol or polycaprolactone polyol.

  The acrylic polymer, which is a preferred example of the specific polymer of the component (D), is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, or a vinyl compound. Any polymer can be used as long as it is a polymer obtained by polymerizing a monomer containing a monomer having the following specific functional group D or a mixture thereof, and the types of main chain skeleton and side chains of the polymer constituting the acrylic polymer It is not particularly limited.

  Examples of the monomer having the specific functional group D include a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxy group, a monomer having a carboxyl group, and an amino group. And a monomer having an alkoxysilyl group, a monomer having an acetoacetoxy group, and a monomer having an amide group.

Examples of the above-mentioned monomer having a polyethylene glycol ester group include H-(OCH ₂ CH ₂ )p-OH monoacrylate or monomethacrylate. The value of p is 2 to 50, preferably 2 to 10.

  Examples of the above-mentioned monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate and 4-hydroxybutyl acrylate. , 4-hydroxybutyl methacrylate.

  Examples of the above-mentioned monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.

  Examples of the above-mentioned monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinyl benzoic acid.

  Examples of the above-mentioned monomer having an amino group in its side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.

  Examples of the above-mentioned monomer having an alkoxysilyl group in the side chain include, for example, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane. Examples thereof include silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyltriethoxysilane.

  Examples of the above-mentioned monomer having an acetoacetoxy group in its side chain include 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate.

  In addition, in the present embodiment, when synthesizing an acrylic polymer which is an example of the component (D), a monomer having no specific functional group D, such as a hydroxy group or a carboxyl group, is used as long as the effects of the present invention are not impaired. A monomer having no group, amide group, amino group, alkoxysilyl group or acetoacetoxy group can be used in combination.

  Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

  Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Examples thereof include propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Examples include propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

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

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

  Examples of vinyl compounds include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

  The amount of the monomer having the specific functional group D used to obtain the acrylic polymer which is an example of the component (D) is based on the total amount of all monomers used to obtain the acrylic polymer which is the component (D). It is preferably 2 mol% to 98 mol %. When the amount of the monomer having the specific functional group D is too small, the liquid crystal alignment of the obtained cured film tends to be insufficient, and when it is too large, the compatibility with the component (A) tends to decrease.

  The method for obtaining the acrylic polymer, which is an example of the component (D), is not particularly limited. For example, a monomer containing a monomer having a specific functional group D, a monomer not having the specific functional group D, and a polymerization initiator may be used. And the like are coexistent in a solvent, and the polymerization reaction is performed at a temperature of 50°C to 110°C. At that time, the solvent used is not particularly limited as long as it dissolves the monomer having the specific functional group D, the optional monomer not having the specific functional group D, the polymerization initiator and the like. Specific examples are described in the section [solvent] described later.

  The acrylic polymer as an example of the component (D) obtained by the above method is usually in the state of a solution dissolved in a solvent.

  Further, a solution of an acrylic polymer, which is an example of the component (D) obtained by the above method, is reprecipitated by adding it to stirring diethyl ether, water or the like, and after filtering and washing the generated precipitate, It can be dried at room temperature or by heating under normal pressure or reduced pressure to obtain an acrylic polymer powder as an example of the component (D). By the above operation, the polymerization initiator and unreacted monomer that coexist with the acrylic polymer which is an example of the component (D) can be removed, and as a result, the purified acrylic polymer which is an example of the component (B). Powder is obtained. If the powder cannot be sufficiently purified by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  The acrylic polymer which is a preferred example of the component (D) has a weight average molecular weight of preferably 3,000 to 200,000, more preferably 4,000 to 150,000, and 5,000 to 100. More preferably, it is 1,000. If the weight average molecular weight is more than 200,000 and is too large, the solubility in a solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 3,000, the heat resistance may be too low. At the time of curing, curing may be insufficient and solvent resistance and heat resistance may decrease. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. The same applies hereinafter in this specification.

  Next, as a polyether polyol which is a preferable example of the specific polymer of the component (D), polyethylene glycol, polypropylene glycol, propylene glycol, polyhydric alcohol such as bisphenol A, triethylene glycol or sorbitol, propylene oxide or polyethylene glycol is used. , Polypropylene glycol and the like are added. Specific examples of the polyether polyol include ADEKA CORPORATION ADEKA POLYETHER P series, G series, EDP series, BPX series, FC series, CM series, NOF Corporation's UNIOX (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA. -700, DB-400, Nonion (trademark) LT-221, ST-221, OT-221 etc. are mentioned.

  The polyester polyol, which is a preferred example of the specific polymer as the component (D), is a polyvalent carboxylic acid such as adipic acid, sebacic acid or isophthalic acid, and a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol or polypropylene glycol. What reacted. Specific examples of the polyester polyol include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240 and OD-X manufactured by DIC Corporation. -668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523. , OD-X-2555, OD-X-2560, Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510 manufactured by Kuraray Co., Ltd. , F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.

  The polycaprolactone polyol, which is a preferred example of the specific polymer of the component (D), includes those obtained by ring-opening polymerization of ε-caprolactone with a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of the polycaprolactone polyol include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC Corporation, Praxel (registered trademark) 205, L205AL manufactured by Daicel Corporation. 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like.

  Polycarbonate polyol, which is a preferred example of the specific polymer as the component (D), includes those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Specific examples of the polycarbonate polyol include Praxel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Corporation, C-590, C-1050, C-2050, C-2090, and C-3090 manufactured by Kuraray Co., Ltd. Etc.

  Cellulose, which is a preferred example of the specific polymer as the component (D), includes hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose. Etc., and hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

  The cyclodextrin which is a preferred example of the specific polymer of the component (D) includes cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin and Methylated cyclodextrins such as methyl-γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxy Ethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxy Propyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin And hydroxyalkyl cyclodextrins such as 2,3-dihydroxypropyl-γ-cyclodextrin.

  The melamine formaldehyde resin, which is a preferred example of the specific polymer of the component (D), is a resin obtained by polycondensing melamine and formaldehyde and is represented by the following formula.

In the above formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and q is a natural number representing the number of repeating units.

  In the melamine-formaldehyde resin as the component (D), it is preferable that the methylol group produced during the polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.

  The method for obtaining the melamine formaldehyde resin as the component (D) is not particularly limited, but generally, melamine and formaldehyde are mixed, made weakly alkaline with sodium carbonate, ammonia, etc., and then heated at 60°C to 100°C. It is synthesized by Further, the methylol group can be alkoxylated by reacting with alcohol.

  The weight average molecular weight of the melamine formaldehyde resin as the component (D) is preferably 250 to 5,000, more preferably 300 to 4,000, and further preferably 350 to 3,500. If the weight average molecular weight is more than 5,000 and is too large, the solubility in a solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 250 and is too small, it may be insufficient during heat curing. Insufficient curing may result in insufficient improvement in solvent resistance and heat resistance.

  In the embodiment of the present invention, the melamine formaldehyde resin as the component (D) may be used in a liquid form or in a solution form in which a purified liquid is redissolved in a solvent described later.

  Examples of the phenol novolac resin which is a preferable example of the specific polymer as the component (D) include phenol-formaldehyde polycondensate.

  In the cured film forming composition of the present embodiment, the polymer of the component (D) may be used in the form of powder or in the form of a solution in which purified powder is redissolved in a solvent described later.

  The content of the component (D) in the cured film-forming composition of the present invention is preferably 400 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent as the component (B). , More preferably 10 parts by mass to 380 parts by mass, further preferably 40 parts by mass to 360 parts by mass. If the content of the component (D) is too large, the liquid crystal alignment tends to deteriorate, and if it is too small, the adhesion tends to decrease.

  Further, in the cured film forming composition of the present embodiment, the component (D) may be a mixture of plural kinds of polymers exemplified as the component (D).

<(E) component>
The cured film forming composition of the present invention may further contain a crosslinking catalyst as a component (E) in addition to the components (A), (B), (C) and/or (D). ..
As the crosslinking catalyst that is the component (E), for example, an acid or a thermal acid generator can be preferably used. The component (E) is effective in promoting the thermosetting reaction of the cured film forming composition of the present invention.
Specific examples of the component (E) include a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof as the above acid. The thermal acid generator is not particularly limited as long as it is a compound that thermally decomposes to generate an acid during heat treatment, that is, a compound that thermally decomposes to generate an acid at a temperature of 80°C to 250°C. ..

  Specific examples of the acid include hydrochloric acid or a salt thereof; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphor. Sulfonic 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, Sulfonic group-containing compounds such as 1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, or The hydrate, the salt, etc. are mentioned.

  Examples of compounds that generate an acid by heat include, for example, bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3. -Phenylene tris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid 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, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate , N-ethyl-p-toluenesulfonamide, and a compound represented by the following formula:

等が挙げられる。

Etc.

  The content of the component (E) in the cured film-forming composition of the present invention is preferably 0.01 parts by mass with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent as the component (B). Parts to 20 parts by mass, more preferably 0.1 parts by mass to 15 parts by mass, still more preferably 0.5 parts by mass to 10 parts by mass. When the content of the component (E) is 0.01 part by mass or more, sufficient thermosetting property and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, the storage stability of the composition may decrease.

<Solvent>
The cured film forming composition of the present invention is mainly used in a solution state in which it is dissolved in a solvent. The solvent used at that time can dissolve the component (A), the component (B), the component (C) and/or the component (D), and if necessary, the component (E) and/or other additives described below. Of course, its type and structure are not particularly limited.

  Specific examples of the solvent include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol 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-hydroxy. Ethyl-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, 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 Etc.

  When a cured film is formed on a resin film by using the cured film forming composition of the present invention to produce an alignment material, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol is used. , 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable from the viewpoint that the resin film is a solvent having resistance.

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

<Other additives>
Furthermore, the cured film-forming composition of the present invention, as long as it does not impair the effects of the present invention, if necessary, adhesion improver, silane coupling agent, surfactant, rheology modifier, pigment, dye, storage stability. Agents, antifoaming agents, antioxidants and the like can be contained.

<Preparation of cured film-forming composition>
The cured film forming composition of the present invention contains a polymer as a component (A), a crosslinking agent as a component (B) and an adhesion promoter as a component (C) and/or a polymer having a thermally crosslinkable group as a component (D). However, the composition can optionally contain a crosslinking catalyst of the component (E), and other additives as long as the effects of the present invention are not impaired. And, usually, they are used in the form of a solution in which they are dissolved in a solvent.

Preferred examples of the cured film forming composition of the present invention are as follows.
[1]: Component (A), based on 100 parts by weight of component (A), 1 part by weight to 300 parts by weight of component (B), and a polymer that is component (A) and a crosslinking agent for component (B). A cured film forming composition containing at least one of 0.1 parts by mass to 100 parts by mass of the component (C) and 1 part by mass to 400 parts by mass of the component (D) per 100 parts by mass of the total amount.
[2]: Based on 100 parts by weight of the component (A) and the component (A), a total of 1 part by weight to 300 parts by weight of the component (B), the polymer that is the component (A) and the crosslinking agent of the component (B). A cured film-forming composition containing 0.1 part by mass to 100 parts by mass of component (C) and 1 part by mass to 400 parts by mass of component (D), and a solvent, relative to 100 parts by mass of the amount. object.
[3]: Based on 100 parts by weight of the component (A) and the component (A), a total of 1 part by mass to 300 parts by mass of the component (B), the polymer that is the component (A) and the crosslinking agent of the component (B). At least one of 0.1 parts by mass to 100 parts by mass of the component (C) and 1 part by mass to 400 parts by mass of the component (D) with respect to 100 parts by mass of the amount of the polymer, which is the component (A), and (B). ) A cured film-forming composition containing 0.01 to 20 parts by mass of the component (E) and a solvent, relative to 100 parts by mass of the total amount of the crosslinking agent.
[4]: Based on 100 parts by weight of the component (A) and the component (A), a total of 1 part by weight to 300 parts by weight of the component (B), the polymer that is the component (A) and the crosslinking agent of the component (B). 1 to 100 parts by mass per 100 parts by mass of the total amount of 0.1 parts by mass to 100 parts by mass of the component (C), the polymer as the component (A) and the crosslinking agent of the component (B). 0.01 to 20 parts by mass of component (E), and 400 parts by mass of component (D), 100 parts by mass of the total amount of the polymer that is component (A) and the crosslinking agent of component (B), and A cured film-forming composition containing a solvent.

The compounding ratio, the 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 the solvent, but is 1% by mass to 60% by mass, preferably 2%. It is from 50% by mass to 50% by mass, more preferably from 2% by mass to 20% by mass. Here, the solid content refers to all components of the cured film-forming composition excluding the solvent.

  The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, a solution of the component (A) dissolved in a solvent is mixed with the component (B), the component (C) and/or the component (D), and further the component (E) at a predetermined ratio, Examples include a method of forming a uniform solution, and a method of further adding and mixing other additives as needed at an appropriate stage of this preparation method.

  In the preparation of the cured film forming composition of the present invention, the solution of the specific copolymer (polymer) obtained by the polymerization reaction in the solvent can be used as it is. In this case, for example, the component (B), the component (C), the component (D), and the component (E) are added to the solution of the component (A) as described above to form a uniform solution. At this time, a solvent may be additionally added for the purpose of adjusting the concentration. At this time, the solvent used in the production process of the component (A) and the solvent used for adjusting the concentration of the cured film forming composition may be the same or different.

  The prepared solution of the cured film-forming composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Cured film, alignment material and retardation material>
The solution of the cured film-forming composition of the present invention is used as a substrate (also referred to as a substrate) (for example, a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass). Substrate, quartz substrate, ITO substrate, etc.) and film substrate (for example, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET)) A film such as a film, an acrylic film, or a resin film such as a polyethylene film) is coated by bar coating, spin coating, flow coating, roll coating, slit coating, slit-based spin coating, inkjet coating, printing, etc. Then, a cured film can be formed by heating and drying with a hot plate or an oven. The cured film can be directly applied as an alignment material.

  The heating and drying conditions may be such that the crosslinking reaction by the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) do not elute into the polymerizable liquid crystal solution applied thereon, for example, at a temperature of 60° C. The heating temperature and the heating time are appropriately selected from the range of 200° C. and the time of 0.4 minutes to 60 minutes. The heating temperature and the heating time are preferably 70° C. to 160° C. and 0.5 minutes to 10 minutes.

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

  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 alignment property is applied onto this alignment material. , Can be oriented on the alignment material. Then, the retardation material in the aligned state is cured as it is, whereby the retardation material can be formed as a layer having optical anisotropy. When the substrate forming the alignment material is a film, it is useful as a retardation film.

  In addition, two substrates having the alignment material of the present invention formed as described above are used, and the alignment materials on both substrates are bonded to each other through a spacer, and then the substrates are bonded between the substrates. It is also possible to inject a liquid crystal to form a liquid crystal display device in which the liquid crystal is aligned.

  As described above, the cured film forming composition of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display elements and the like.

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

[Symbols used in Examples]
The meanings of the abbreviations used in the following examples are as follows.

<Raw materials for each component>
jER-1001: Bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, molecular weight 900
jER-1055: Mitsubishi Chemical Corporation bisphenol A type epoxy resin, molecular weight 1,600
jER-157S70: Mitsubishi Chemical Co., Ltd. epoxidized bisphenol A novolac resin ECN-1299: Asahi Kasei Co., Ltd. cresol novolac resin EHPE-3150: Daicel trimethylolpropane 1,2-epoxy-4-( 2-Oxiranyl)cyclohexane adduct LAUA: lauric acid 5CCA: 4-(4'-pentyl-[1,1'-bi(cyclohexane)]-4-carboxylic acid BMAA: N-butoxymethylacrylamide BTEAC: benzyltriethylammonium chloride AIBN: α,α′-azobisisobutyronitrile HEMA: 2-hydroxyethyl methacrylate MMA: methyl methacrylate

<(B) component>
HMM: Melamine cross-linking agent represented by the following structural formula [CYMEL (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.]]

<(C) component>
BMAA: N-butoxymethylacrylamide DM-1:

<(D) component>
PUA: Polyurethane graft acrylic polymer [Acryt (registered trademark) 8UA-146 (manufactured by Taisei Fine Chemical Co., Ltd.)]
PCDO: Polycarbonate diol [C-590 (manufactured by Kuraray Co., Ltd.)]
PEPO: Polyester polyol polymer (adipic acid/diethylene glycol copolymer having the following structural unit. Molecular weight 4,800)

（上記式中、Ｒは、アルキレンを表す。）

(In the above formula, R represents alkylene.)

<(E) component>
PTSA: p-toluenesulfonic acid monohydrate

<Solvent>
PM: Propylene glycol monomethyl ether BA: Butyl acetate MEK: Methyl ethyl ketone CPME: Cyclopentyl methyl ether

  The number average molecular weight and the weight average molecular weight of the acrylic copolymer obtained according to the following synthesis example were measured using a GPC device (SHODX (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation, and an elution solvent of tetrahydrofuran at a flow rate of 1 mL. The measurement was carried out under the condition that the sample was eluted by flowing it through the column (column temperature 40° C.) at a flow rate of /min. The number average molecular weight (hereinafter, referred to as Mn) and the weight average molecular weight (hereinafter, referred to as Mw) described below are expressed in terms of polystyrene.

<Synthesis of component (A)> (1)
<Synthesis example 1>
jER-1001 50.0 g, LAUA 6.25 g, and BTEAC 0.14 g were melt|dissolved in PM 131.58 g, and it was made to react at 110 degreeC for 16 hours, and the vertical alignment polymer (solid content concentration 30 mass%) (PA1) was obtained. Obtained. The epoxy value of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group had disappeared in the amount that LAUA was completely reacted.

<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 a vertical alignment polymer (solid content concentration 30 mass%) (PA2) was obtained by reacting at 110° C. for 16 hours. Obtained. The epoxy value of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group had disappeared in the amount that LAUA was completely reacted.

<Synthesis example 3>
jER-157S70 50.0 g, LAUA 14.3 g, and BTEAC 0.33 g were dissolved in PM 150.8 g, and the vertical alignment polymer (solid content concentration 30 mass%) (PA3) was obtained by reacting at 110° C. for 16 hours. Obtained. The epoxy value of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group corresponding to the total reaction of LAUA had 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 a vertical alignment polymer (solid content concentration 30 mass%) (PA4) was obtained by reacting at 110° C. for 16 hours. Obtained. The epoxy value of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group had disappeared in the amount that LAUA was completely reacted.

<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 give a vertically aligned polymer (solid content 30% by mass) (PA5). Obtained. The epoxy value of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group corresponding to the total reaction of LAUA had disappeared.

<Synthesis example 6>
jER-1001 50.0 g, 5CCA 8.88 g, and BTEAC 0.14 g were dissolved in PM 137.73 g and reacted at 110° C. for 16 hours to give a vertical alignment polymer (solid content concentration 30% by mass) (PA6). Obtained. The epoxy value of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy groups corresponding to all of the 5CCA had disappeared.

<Synthesis of component (B)> (1)
<Synthesis example 7>
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% by mass) (PB1). .. The acrylic copolymer obtained had Mn of 4,800 and Mw of 3,100.
<Synthesis of component (C)>

<Synthesis example 8>
32.0 g of BMAA, 8.0 g of GMA, and 0.8 g of AIBN as a polymerization catalyst were dissolved in 204.0 g of tetrahydrofuran and reacted at 60° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PC1). The obtained acrylic copolymer had Mn of 7,000 and Mw of 18,000.

<Synthesis example 9>
10.0 g of the acrylic copolymer (PC1) obtained in Synthesis Example 7, 2.2 g of acrylic acid, 0.2 g of dibutylhydroxytoluene, 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM and reacted at 90° C. for 20 hours. Let This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PC2) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PC2) had an acroyl group.
The PC2 also acts as the component (B) in the present invention.

Synthesis of compound [DM-1]

  Under a nitrogen stream, 500 g of ethyl acetate, 35.5 g (0.300 mol) of 1,6-hexanediol and 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) 1 were placed in a 2 L four-necked flask. .80 g (11.8 mmol) and 2,6-di-tert-butyl-para-cresol (BHT) 0.45 g (2.04 mmol) were charged at room temperature, and the temperature was raised to 55° C. under magnetic stirring. did. To the reaction solution, 95.9 g (0.679 mol) of 2-isocyanatoethyl acrylate was added dropwise, and after stirring for 2 hours, the reaction solution was analyzed by high performance liquid chromatography, and the intermediate was 1% or less in area percentage. The reaction was completed in the open. After adding 328 g of hexane and cooling to room temperature, the precipitated solid was washed twice with 229 g of hexane and dried to obtain compound [A-a] (104 g, 0.260 mol, yield 86.7%). ..

Under a nitrogen stream, 1330 g of dichloromethane, 100 g (0.250 mol) of compound [A-a] and 22.5 g (0.749 mol) of paraformaldehyde were charged to a 2 L four-necked flask, and 122 g of trimethylsilyl chloride (1. 12 mol) was added dropwise. After stirring for 2 hours, a mixed solution of 63.2 g (0.625 mol) of triethylamine and 240 g of methanol was added dropwise. After stirring for 30 minutes, the mixture was transferred to a 5 L separating funnel and 1500 g of water was added to carry out a liquid separating operation. The obtained organic layer was dried over magnesium sulfate, and the filtrate obtained by removing magnesium sulfate by filtration was concentrated and dried to obtain compound [DM-1] (110 g, 0.226 mol, yield 90. 3%). The structure of the compound [DM-1] was confirmed by ¹ H-NMR analysis by obtaining the following spectrum data.
¹ H-NMR (CDCl ₃ ): δ 6.42 (d, 2H J=17.2), 6.17-6.08 (m, 2H), 5.86 (d, 2H J=10.0), 4.77 (d, 4H J = 19.6), 4.30 (m, 4H), 4.12 (t, 4H J = 6.4), 3.61 (m, 4H), 3.30 ( d, 6H J=12.8), 1.67 (m, 4H), 1.40 (m, 4H).

<Synthesis of component (D)>
<Synthesis example 10>
MMA 100.0 g, HEMA 11.1 g, and AIBN 5.6 g as a polymerization catalyst were dissolved in PM 450.0 g and reacted at 80° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration 20% by mass) (PD1 ) Got. Mn of the obtained acrylic copolymer was 4,200 and Mw was 7,600.

<Synthesis of component (A)> (2)
<Synthesis example 11>
A vertical alignment polymer (solid content 20% by mass) (PA7) was obtained by dissolving 44.2 g of EHPE-3150, 15.4 g of LAUA and 0.44 g of BTEAC in 240.0 g of PM and reacting at 110° C. for 16 hours. Obtained. The epoxy value of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group had disappeared in the amount that LAUA was completely reacted.

<Synthesis example 12>
40.1 g of EHPE-3150, 19.5 g of 5CCA and 0.40 g of BTEAC were dissolved in 240.0 g of PM, and a vertical alignment polymer (solid content concentration 20% by mass) (PA8) was obtained by reacting at 110° C. for 16 hours. Obtained. The epoxy value of the obtained vertically aligned polymer was measured, and it was confirmed that the epoxy group corresponding to the total reaction of A5 disappeared.

<Synthesis of component (B)> (2)
<Synthesis example 13>
100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst were dissolved in 193.5 g of PM, and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration 35% by mass) (PB2). The obtained acrylic copolymer had Mn of 2,700 and Mw of 3,900.

<Creation of base film>
The acrylic film used as the base material can be produced, for example, by the following method. That is, a raw material pellet made of a copolymer containing methyl methacrylate as a main component is melted at 250° C. by an extruder and passed through a T-die, and a 40 μm-thick acrylic film is prepared through a casting roll and a drying roll. can do.

<Examples and comparative examples>
The cured film forming compositions of Examples and Comparative Examples were prepared with the compositions shown in Table 1. In addition, the compounding amounts of the components (A) to (E) in Table 1 are all in terms of solid content (excluding the solvent when obtained as a solution during preparation). Next, each retardation material forming composition was used to form a cured film, and each of the obtained cured films was evaluated for vertical alignment and adhesion.

[Evaluation of vertical orientation]
<Examples 1 to 18, Comparative Examples 1 to 4>
Each of the cured film forming compositions of Examples 1 to 18 and Comparative Examples 1 to 4 was applied onto the base material shown in Table 2 or Table 3 with a Wet film thickness of 4 μm using a bar coater. Then, each was heat-dried at a temperature of 110° C. for 60 seconds in a heat-circulation oven to form a cured film on each substrate.
On the cured film, a vertical alignment polymerizable liquid crystal solution RMS03-015 manufactured by Merck Ltd. was applied with a Wet film thickness of 6 μm using a bar coater. The coating film on this substrate was exposed at 600 mJ/cm ² to prepare a retardation material.
The incident angle dependence of the in-plane retardation of these manufactured retardation materials was measured using a retardation measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. Those in which the in-plane retardation value at an incident angle of 0 degree was 0 and the in-plane retardation value at an incident angle of ±50 degrees was 38±5 nm were judged to be vertically aligned. Table 2 shows the evaluation results of Examples 1 to 15 and Comparative Examples 1 and 2 as “vertical orientation”, and Table 3 shows the evaluation results of Examples 16 to 18 and Comparative Examples 3 and 4.

[Evaluation of adhesion]
<Examples 1 to 15 and Comparative Examples 1 to 2>
Each of the cured film forming compositions of Examples and Comparative Examples was applied onto the base material shown in Table 2 with a Wet film thickness of 4 μm using a bar coater. Then, each was heat-dried at a temperature of 110° C. for 60 seconds in a heat-circulation oven to form a cured film on each substrate.
On the cured film, a vertical alignment polymerizable liquid crystal solution RMS03-015 manufactured by Merck Ltd. was applied with a Wet film thickness of 6 μm using a bar coater. The coating film on this substrate was exposed at 600 mJ/cm ² to prepare a retardation material.
The retardation material was cut with a cutter knife so as to form 5×5 squares at intervals of 1 mm in length and width. A cellophane tape peeling test was performed on the cuts using Scotch tape. In the evaluation, all the 25 squares remaining without being peeled off were evaluated as ◯, and even one square was peeled off as x. The evaluation results are shown later in Table 2 as "adhesion".

As shown in Table 2, the alignment materials obtained by using the cured film forming compositions of Examples 1 to 15 are the same as the alignment materials obtained by using the cured film forming compositions of Comparative Examples 1 and 2. And showed good vertical alignment. Further, as shown in Table 3, the alignment materials obtained by using the cured film forming compositions of Examples 16 to 18 are compared with the alignment materials obtained by using the cured film forming compositions of Comparative Examples 3 and 4. It showed good vertical orientation on various substrates.
Moreover, the cured film obtained using the cured film forming composition of Examples 1-15 showed the outstanding adhesiveness. On the other hand, it was difficult for the cured film obtained by using the cured film forming compositions of Comparative Examples 1 and 2 to obtain adhesiveness.

  The cured film forming composition according to the present invention is very useful as a material for forming an alignment material for forming a liquid crystal alignment film of a liquid crystal display device or an optically anisotropic film provided inside or outside the liquid crystal display device. In particular, it is suitable as a material for an optical compensation film of IPS-LCD.

Claims (9)

(A) an epoxy group of the epoxy group of the polymer having one or more side chain or end, a polymer in which a carboxyl group is reacted with the carboxyl group of the compound bound to a vertical alignment group, (B) a methylol group or an alkoxy It has a cross-linking agent having a methyl group, and (C) an adhesion promoter selected from a monomer and a polymer having a group selected from a hydroxy group and an N-alkoxymethyl group, and a polymerizable group, and (D) a heat-crosslinkable group. A cured film-forming composition containing any one or both of polymers,
The vertical orientation group is an alkyl group having 6 to 20 carbon atoms, or the following formula [1]:

(In formula [1],
* Represents the bond position,
Y ^{1 to} Y ⁴ represent a single bond ,
Y ⁵ represents a divalent cyclic group selected et or benzene ring and cyclohexane ring,
n represents an integer of 2 to 3 , and when n is 2 or more, Y ^{5 s} may be the same or different,
Y ⁶ is to display the carbon atom number 1-18 alkyl group. ) A cured film-forming composition, which is a group represented by:
However, in the above definition, the polymer having a methylol group or an alkoxymethyl group is the component (B),
A monomer and a polymer having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group are components (C). The cured film-forming composition according to claim 1, wherein the polymer having one or more epoxy groups on a side chain or a terminal is a polymer having a ring structure in the main chain and having a number average molecular weight of 300 to 20,000. The polymer having at least one epoxy group on the side chain or terminal is a bisphenol A type epoxy resin, a bisphenol F epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A novolac type epoxy resin and a polyol. The cured film forming composition according to claim 1 or 2, which is any one polymer selected from the group consisting of a 2-epoxy-4-(2-oxiranyl)cyclohexane adduct. (E) a cured film forming composition according to any one of claims 1 to 3 further contains a crosslinking catalyst. The cured film forming composition according to any one of claims 1 to 4 , which contains 1 part by mass to 300 parts by mass of the component (B) based on 100 parts by mass of the component (A). 0.1 parts by mass to 100 parts by mass of the component (C) and 1 part by mass to 400 parts by mass of (D) per 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent as the component (B). ) The cured film forming composition according to any one of claims 1 to 5 , containing either one or both of the components. (A) any one of claims 4 to 6 containing the ingredients in a polymer and (B) component crosslinking agent total amount of 0.01 parts by 20 weight parts with respect to 100 parts by weight of component (E) The cured film-forming composition according to item 1. An alignment material obtained by curing the composition for forming a cured film according to any one of claims 1 to 7 . A retardation material, which is formed using a cured film obtained from the cured film forming composition according to any one of claims 1 to 7 .