KR102406797B1 - Cured-film-forming composition, alignment material, and phase difference material - Google Patents

Abstract

[Problem] It has excellent vertical orientation, transparency and solvent resistance required for optical compensation film, and furthermore, it has adhesion to the substrate and polymerizable liquid crystal layer, and it is stably polymerizable even on a resin film under low-temperature and short-time firing conditions. To provide a cured film forming composition for providing an alignment material that can vertically align liquid crystals.
[Solutions] (A) a polymer in which a carboxyl group and a carboxyl group of a compound having a vertical orientation group are reacted with the epoxy group of a polymer having one or more epoxy groups in the side chain or at the terminal, (B) a crosslinking agent and (C) an adhesion promoter and (D) ) A cured film forming composition comprising any one or both of the polymers having a thermally crosslinkable group, an orientation material obtained using the composition, and a retardation material obtained using the composition.

Description

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

The present invention relates to a cured film forming composition suitable for a vertical alignment material for vertically aligning 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 having positive dielectric anisotropy (Δε > 0). It relates to a cured film forming composition useful for preparing a +C plate (positive C plate), an orientation material, and a retardation material, which are used to improve the viewing angle characteristics of an orientation switching LCD).

IPS-LCD is characterized by little change in luminance/color due to viewing angle because there is no vertical inclination of liquid crystal molecules. For example, as disclosed in Patent Document 1, in the IPS-LCD at the early stage of the proposal, the compensation film of the viewing angle is not used, and in the IPS-LCD that does not use the compensation film of the viewing angle, the angle of inclination is dark. There is a disadvantage in that a value of a low contrast ratio is exhibited because of a relatively large light leakage in the present invention.

Patent Document 2 discloses an IPS-LCD compensation film using a +C plate and a +A plate (positive A plate). In this document, the following structures are shown with respect to the liquid crystal display element described there.

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

2) At least one +A plate and +C plate are sandwiched between both polarizers.

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

4) The phase difference value R _LC of the liquid crystal layer, the phase difference value R _+C of the +C plate, and the phase difference value R _+A of the +A plate are determined to satisfy the following equations.

R _LC :R _+C :R _+A ≒1:0.5:0.25

5) The relation between the retardation values in the thickness direction of the protective film of the polarizing plate with respect to the retardation values of the +A plate and the +C plate is not shown (TAC, COP, PNB).

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

Japanese Patent Laid-Open No. H02-256023 Japanese Patent Laid-Open No. H11-133408 Japanese Patent Laid-Open No. 2009-122715 Japanese Patent Laid-Open No. 2001-281669

As previously proposed, the +C plate can compensate for light leakage in a place where the viewing angle of the polarizing plate is large, and thus is very useful as an optical compensation film for IPS-LCDs. However, it is difficult to develop vertical alignment (positive C plate) properties in the conventionally generally known method of stretching.

Moreover, the vertical alignment film|membrane using the polyimide proposed conventionally needs to use the solvent of polyimides, such as N-methyl-2-pyrrolidone, in film|membrane preparation. Accordingly, there is no problem in the glass substrate, but when the substrate is a film, there is a problem in that the substrate is damaged during the formation of the alignment layer. Moreover, in the vertical alignment film using polyimide, baking at high temperature is required, and there exists a problem that a film base material cannot withstand high temperature.

Furthermore, a method of forming a vertical alignment film has been proposed by directly treating the substrate with a silane coupling agent having a long-chain alkyl or the like, but if there is no hydroxyl group on the surface of the substrate, the processing is difficult and the substrate is limited. (Patent Document 4).

The present invention has been made based on the above knowledge and examination results, and the problem to be solved is that it has excellent vertical orientation, transparency and solvent resistance required for an optical compensation film, and furthermore, a substrate and a polymerizable liquid crystal layer and It is to provide a cured film forming composition for providing an alignment material that has the adhesion of and can vertically orient the polymerizable liquid crystal stably even on a resin film under low-temperature and short-time firing conditions.

Another object of the present invention is an alignment material obtained from the cured film-forming composition, having excellent vertical orientation, and capable of stably aligning a polymerizable liquid crystal vertically even on a resin film under low-temperature and short-time firing conditions, and its It is to provide a phase difference material useful for the +C plate formed using an orientation material.

In order to achieve the above object, the present inventors, as a result of repeated studies, select a cured film forming material based on an acrylic copolymer having a long-chain alkyl group in the side chain, thereby providing excellent vertical orientation and And it discovered that the cured film which has adhesiveness with a polymeric liquid crystal layer could be formed, and this invention was completed.

That is, the present invention is a first aspect,

(A) a polymer in which a carboxyl group and a carboxyl group of a compound having a vertical orientation group are reacted with the epoxy group of a polymer having one or more epoxy groups in the side chain or at the terminal, (B) a crosslinking agent, and

(C) any one or both of the adhesion promoter and (D) a polymer having a thermally crosslinkable group

As a cured film forming composition containing,

The vertical alignment group relates to a cured film forming composition, characterized in that the group represented by the following formula [1].

[Formula 1]

(in formula [1],

* indicates a bonding position,

Y ¹ represents a single bond,

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

Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms,

Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, or a divalent organic group having a steroid skeleton with 17 to 30 carbon atoms, and any hydrogen on the cyclic group A valence, an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms or a fluorine atom may be substituted,

Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atoms on these cyclic groups are an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or 1 carbon atom. It may be substituted with a fluorine-containing alkyl group of ~3, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms or a fluorine atom,

n represents an integer of 0 to 4, and when n is 2 or more, Y ⁵ may be the same or different,

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

The alkylene group as Y ² and Y ³ , and the substituent on the cyclic group or the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxy group as Y ⁶ may be linear, branched, or cyclic any one or a combination thereof. there is,

In addition, the alkylene group as Y ² and Y ³ , and the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxy group as Y ⁶ may be interrupted by 1 to 3 bonding groups, unless the bonding groups are adjacent to each other,

Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group having a steroid skeleton, Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or fluorine When the containing alkyl group is represented, the divalent cyclic group, the divalent organic group having this steroid skeleton, the alkylene group, the alkyl group and the fluorine-containing alkyl group may be bonded to adjacent groups via a bonding group,

And the bonding group is -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH- represents a group selected from the group consisting of,

However, 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, an alkyl group having 1 to 18 carbon atoms, and 1 to carbon atoms. The total number of carbon atoms in the fluorine-containing alkyl group of 18, 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 2nd viewpoint, the polymer which has one or more said epoxy groups in a side chain or a terminal is a polymer with a number average molecular weight 300-20,000 which has a ring structure in a main chain, It relates to the cured film formation composition of a 1st viewpoint.

As a third aspect, the polymer having at least one epoxy group in the side chain or terminal is bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy It relates to the cured film forming composition according to the first or second viewpoint, which is any one type of polymer selected from the group consisting of 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of resins and polyols. will be.

As a 4th viewpoint, it is related with the cured film formation composition in any one of a 1st viewpoint thru|or a 3rd viewpoint whose crosslinking agent of (B) component is a crosslinking agent which has a methylol group or an alkoxymethyl group.

As a 5th viewpoint, it is related with the cured film formation composition in any one of 1st viewpoint thru|or 4th viewpoint which further contains (E) a crosslinking catalyst.

As a 6th viewpoint, based on 100 mass parts of (A) component, it is related with the cured film formation composition in any one of 1st viewpoint - 5th viewpoint containing 1 mass part - 300 mass parts (B) component.

As a 7th viewpoint, any of 0.1 mass parts - 100 mass parts (C)component and 1 mass part - 400 mass parts (D)component with respect to 100 mass parts of total amounts of the crosslinking agent of the polymer which is (A) component, and (B) component It relates to the cured film formation composition in any one of a 1st viewpoint thru|or a 6th viewpoint containing one or both.

As an 8th viewpoint, it is related with the cured film formation composition in any one of a 5th viewpoint - 7th viewpoint containing 0.01 mass part - 20 mass parts (E) component.

It is obtained by hardening the cured film formation composition in any one of a 1st viewpoint thru|or an 8th viewpoint as a 9th viewpoint, It is related with the orientation material characterized by the above-mentioned.

It is formed using the cured film obtained from the cured film formation composition in any one of a 1st viewpoint thru|or an 8th viewpoint as a 10th viewpoint, It is related with the retardation material characterized by the above-mentioned.

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

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

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

<Cured film forming composition>

The cured film forming composition of the present invention is (A) a polymer in which the carboxyl group of a compound having a carboxyl group and a vertical orientation group is reacted with the epoxy group of the polymer having one or more epoxy groups in the side chain or terminal, (B) a crosslinking agent, and (C) ) contain any one or both of an adhesion promoter and (D) a polymer having a thermally crosslinkable group. In addition to the said (A) component, (B) component, (C)component, and (D)component, the cured film formation composition of this invention can also contain a crosslinking catalyst as (E)component further. In addition, other additives may be contained as long as the effects of the present invention are not impaired.

Hereinafter, the detail of each component is demonstrated.

<(A) component>

Component (A) contained in the cured film forming composition of the present invention is a polymer in which the carboxyl group of the compound having a carboxyl group and a vertical alignment group is reacted with the epoxy group of the polymer having one or more epoxy groups in the side chain or terminal. In addition, in the following specification, the polymer of (A) component is also called "vertical orientation polymer".

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

As specific examples of the polymer having one or more epoxy groups in the side chain or at the terminal, for example, polyglycidyl methacrylate, glycidyl methacrylate copolymer, poly (3,4-epoxycyclohexyl methyl methacrylate) ), 3,4-epoxycyclohexylmethylmethacrylate copolymer. Bisphenol A type epoxy resin, bisphenol F epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, 1,2-epoxy-4-(2-oxiranyl of trimethylolpropane) ) cyclohexane adduct, and the like.

Among the polymers having one or more epoxy groups in the side chain or at the terminal, polymers having a ring structure in the main chain are preferable, and specifically, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolac A type epoxy resin, a bisphenol A novolak type epoxy resin, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of a polyol, etc. are preferable at the point which the applicability|paintability of a liquid crystal improves.

As the molecular weight of the polymer having one or more of these epoxy groups in the side chain or the terminal, it is preferable that the number average molecular weight in terms of polystyrene (hereinafter referred to as a number average molecular weight) is 300 to 20,000. Preferably it is 400 to 10,000, More preferably, it is 500 to 8,000.

Commercially available polymers having at least one epoxy group in the side chain or at the terminal can be suitably used, and specific examples of the bisphenol A type epoxy resin include jER1001, jER1002, jER1003, jER1004, jER1055, jER1007, jER1009, jER1010, jER834, jER828 (above, manufactured by Mitsubishi Chemical Co., Ltd.), etc., as a bisphenol F type epoxy resin, jER806, jER807 (above, manufactured by Mitsubishi Chemical Corporation), etc., as a phenol novolak type epoxy resin, jER152 , jER154 (above, manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, EPPN202 (above, manufactured by Nippon Kayaku Co., Ltd.), etc., as a cresol novolak-type epoxy resin, ECN-1299 (manufactured by Asahi Kasei Co., Ltd.), EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku Co., Ltd.), jER80S75 (manufactured by Mitsubishi Chemical Co., Ltd.), etc., bisphenol A novolac As the type epoxy resin, jER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), etc., and as the polyol 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct, EHPE-3150 (manufactured by Daicel) and the like.

In the present specification, the vertical alignment group refers to, for example, a group containing a hydrocarbon group having about 6 to 20 carbon atoms, and specifically refers to a group represented by the following formula [1].

Therefore, as a compound which has a carboxyl group and a vertical orientation group, the compound which has a carboxyl group and a C6-C20 hydrocarbon group is mentioned, for example.

Examples of the hydrocarbon group having 6 to 20 carbon atoms include a hydrocarbon group having 6 to 20 carbon atoms including a linear, branched or cyclic alkyl group or aromatic group having 6 to 20 carbon atoms.

More specifically, the vertical alignment group is a group represented by the following formula [1].

[Formula 2]

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

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

In formula [1], Y< ² > represents a C1-C15 alkylene group or.

Moreover, as Y< ² >, a bivalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring is mentioned, Arbitrary hydrogen atom on these cyclic groups is a C1-C3 alkyl group, C1-C3 alkoxy. It may be substituted with a real group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom.

Examples of the heterocycle include 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 pyridine ring Dazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadia A zole ring, an acridine ring, etc. are mentioned, More preferable are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, They are 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, ethyl group, n-propyl group, isopropyl group, and cyclopropyl group. can be heard Examples of the fluorine-containing alkyl group and the fluorine-containing alkoxyl group include groups in which any hydrogen atom among the alkyl group and the alkoxyl group is substituted with a fluorine atom.

Among these, it is preferable that Y< ² > is a benzene ring or a cyclohexane ring from the point of easy synthesis.

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

In the formula [1], Y ⁴ represents a single bond or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms. , a C1-C3 alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom may be substituted.

The heterocyclic ring and the alkyl group mentioned as ^a substituent can be made into what was mentioned by Y2 mentioned above.

Furthermore, as Y ⁴ , it may be a divalent organic group selected from organic groups having a steroid skeleton as 17 to 30 carbon atoms. Preferred examples thereof include cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estryl, 11α-hydroxymethylsteryl, 11α-proge. Selected from steryl, lanosteryl, melatranil, methyltestosteryl, noretisteryl, pregnenonyl, β-sitosteryl, stigmasteryl, testosteryl, and cholesterol acetate ester It is a divalent group having a structure in which two hydrogen atoms have been removed from the structure to be formed. More specifically, it is as follows, for example.

[Formula 3]

(Wherein, * represents a bonding position with Y ³ and Y ⁵ (or Y ⁶ ).)

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

In formula [1], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocycle, and any hydrogen atoms on these cyclic groups are an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. It may be substituted with 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 a fluorine atom. ^The heterocyclic ring and the alkyl group mentioned as a substituent can be made into what was mentioned by Y4 mentioned above.

Among these, ^it is preferable that Y5 is a benzene ring or a cyclohexane ring.

Moreover, in Formula [1], n represents the integer of 0-4, and when n is 2 or more, the same group or different groups may be sufficient as Y< ⁵ >. Among them, 0 to 3 are preferable for n from the viewpoints of availability of raw materials and easy synthesis. More preferably, it is 0-2.

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

Among them, Y ⁶ is preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms. More preferably, Y ⁶ is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferably, Y ⁶ is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

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

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

For example, the alkyl group is, for example, a methyl group, an 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 group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl- n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1 -Methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1, 3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group , 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2 -Methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2- Methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2 ,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2- Methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-unde Actual group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , n-pentadecyl group, and the like.

As said alkylene group, the bivalent group which removed one arbitrary hydrogen atom from the said alkyl group is mentioned.

As said alkoxyl group, the group which oxygen atom -O- couple|bonded with the group mentioned as a specific example of the said alkyl group is mentioned.

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

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

In addition, the alkylene group as Y ² and Y ³ , and the alkyl group, fluorine-containing alkyl group, alkoxyl group and fluorine-containing alkoxy group as Y ⁶ may be interrupted by 1 to 3 bonding groups as long as the bonding groups are not adjacent to each other.

Further, Y ² , Y ⁴ or Y ⁵ represents a divalent cyclic group, Y ⁴ represents a divalent organic group having a steroid skeleton, Y ² or Y ³ represents an alkylene group, or Y ⁶ represents an alkyl group or When representing a fluorine-containing alkyl group, this divalent cyclic group, this divalent organic group having a steroid skeleton, this alkylene group, this alkyl group, and this fluorine-containing alkyl group may be bonded to adjacent groups via a bonding group.

In addition, the bonding group is -O-, -CH ₂ O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH- and -NH-CO-NH-.

Further, 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, an alkyl group having 1 to 18 carbon atoms, and 1 to carbon atoms. The total number of carbon atoms in the fluorine-containing alkyl group of 18, 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, for example, 6 to 20.

Among these, when vertical alignment and the applicability|paintability of a polymeric liquid crystal are considered, it is preferable that a vertical alignment group is a group containing a C7-18, especially a 8-15 alkyl group.

As a preferable vertical orientation group, a C6-C20 hydrocarbon group is mentioned, for example. Examples of the hydrocarbon group having 6 to 20 carbon atoms include a hydrocarbon group having 6 to 20 carbon atoms including a linear, branched or cyclic alkyl group or aromatic group having 6 to 20 carbon atoms.

As the vertical alignment group, for example, Y ¹ to Y ⁴ is a single bond, Y ³ is a single bond or an alkylene group having 1 to 15 carbon atoms, n is 0, and Y ⁶ is 1 to 18 carbon atoms The group which is an alkyl group is mentioned, Especially, the perpendicularly-oriented group (a-1) whose total number of carbon atoms is an alkyl group whose total number of carbon atoms of the group represented by Formula [1] is preferable. Specific examples of such an alkyl group include an alkyl group having 6 to 20 carbon atoms in total among the aforementioned alkyl groups.

As the vertical alignment group, in addition to the above, for example, Y ¹ to Y ⁴ are a single bond, n is 2 to 3, Y ⁵ is a group selected from a benzene ring and a cyclohexane ring, Y ⁶ is the number of carbon atoms A vertical alignment group (a-2) which is an alkyl group of 1-18 is preferable. As such a group (a-2), the following (a-2-1) - (a-2-6) etc. are preferable.

[Formula 4]

(Wherein, Y ⁶ is an alkyl group having 1 to 18 carbon atoms. In addition, * indicates a bonding position.)

As the vertical alignment group, in addition to the above, for example, Y ¹ to Y ³ are a single bond, Y ⁴ is a steroid skeleton, n is 0, and Y ⁶ is a hydrogen atom. desirable. Examples of the group (a-3) include vertical alignment groups (a-3-1) to (a-3-8) represented by the following formulas.

[Formula 5]

(In the formula, * indicates 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 vertical alignment group.

The vertically oriented polymer of component (A) in the present invention is a polymer in which a carboxyl group and a carboxyl group of a compound having a vertical alignment group are reacted with the epoxy group of the polymer having one or more epoxy groups in the side chain or the terminal described above. When the epoxy group and the carboxyl group react, a bond called -CH ₂ -CH(OH)-CH ₂ - occurs.

To obtain the vertically oriented polymer, the amount of the polymer having at least one epoxy group in the side chain or terminal, and the compound having a carboxyl group and a vertically oriented group, the amount of the epoxy group in the side chain or terminal 1 or more of the polymer having at least one epoxy per equivalent, It is preferable to use so that the carboxyl group of the compound which has a carboxyl group and a vertical orientation group may become 5-60 equivalent.

When the carboxyl group of the compound having a carboxyl group and a vertical alignment group is less than 5 equivalents with respect to 1 equivalent of the epoxy of the polymer having one or more epoxy groups in the side chain or terminal, the desired vertical alignment property in the obtained vertically aligned polymer may not be sufficiently obtained. . In addition, when the carboxyl group of the compound having a carboxyl group and a vertical alignment group exceeds 60 equivalents, a cured film (orientation material) is formed using this vertical alignment polymer, and a polymerizable liquid crystal solution or the like is applied thereon. Applicability of liquid crystal There is a fear that this may decrease (spattering of the liquid crystal may occur).

In addition, a compound having a carboxyl group without containing a vertical alignment group may be reacted with an epoxy residue of a polymer having one or more epoxy groups in a side chain or terminal in which a carboxyl group and a compound having a vertical alignment group are reacted. In that case, the amount of the carboxyl group with respect to 1 equivalent of the epoxy of the polymer having one or more epoxy groups in the side chain or the terminal is the carboxyl group of the compound having a carboxyl group and a vertical alignment group, and the carboxyl group of the compound having a carboxyl group without containing a vertical alignment group. , it is preferable to set it as 5 to 60 equivalents.

The order of obtaining the vertically oriented polymer used in the present invention is not particularly limited, but, for example, a polymer having at least one epoxy group in the side chain or at the terminal, a compound having a carboxyl group and a vertical alignment group, and in some cases, without containing a vertical alignment group It is obtained by making the compound which has a carboxyl group react at the temperature of 50-150 degreeC in the solvent which coexisted the reaction catalyst etc. At this time, the solvent used is not particularly limited as long as it dissolves a polymer having one or more epoxy groups in the side chain or terminal, a compound having a carboxyl group and a vertical orientation group, and a reaction catalyst. As the specific example, what was included in the <solvent> mentioned later can be used suitably. Examples of the reaction catalyst include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetra quaternary ammonium salts such as propylammonium chloride and tetrapropylammonium bromide; quaternary phosphonium salts such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, and ethyltriphenylphosphonium bromide; .

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

In addition, the solution of the vertically oriented polymer obtained in the above method is added to diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed, then dried at room temperature or heat dried under normal pressure or reduced pressure, and vertical It can be set as the powder of an orientation polymer. By the above operation, the reaction catalyst and unreacted compounds coexisting with the vertically aligned polymer can be removed, and as a result, purified powder of the vertically aligned polymer is obtained. What is necessary is just to make the obtained powder re-dissolve in a solvent again and just to perform said operation repeatedly, when it cannot fully refine|purify by one operation.

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

Moreover, in this invention, the mixture of several types of vertical alignment polymers may be sufficient as the vertical alignment polymer of (A) component.

<(B) component>

(B) component in the cured film formation composition of this invention is a crosslinking agent.

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

As a compound which has these groups, methylol compounds, such as an alkoxy methylation glycoluril, the alkoxy methylation benzoguanamine, and an alkoxy methylation melamine, are mentioned, for example.

Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril; 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1 ,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl) ) -4,5-dimethoxy-2-imidazolinone etc. are mentioned. As a commercial product, compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Nippon Cytec Industries (formerly Mitsui Cytec), methylated urea resins ( Product name: UFR (registered trademark) 65), butylated urea resin (product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (formerly Dainippon Inky Chemical Industry Co., Ltd.) )) urea/formaldehyde-based resins (high condensation type, trade names: Beccamine (registered trademark) J-300S, Beccamine P-955, Beccamine N) and the like.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. As a commercial product, manufactured by Nippon Cytec Industries (formerly Mitsui Cytec) (brand name: Cymel (registered trademark) 1123), Sanwa Chemicals (brand name: Nikalac (registered trademark) BX-4000) , Nikalac BX-37, Nikalac BL-60, Nikarac BX-55H) and the like.

As a specific example of the alkoxymethylation melamine, hexamethoxymethylmelamine etc. are mentioned, for example. As a commercial item, a methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Nippon Cytec Industries (formerly Mitsui Cytec), a butoxymethyl type melamine compound (Brand name: Mycoat (registered trademark) 506, 508), Sanwa Chemical Co., Ltd. methoxymethyl type melamine compound (trade name: Nikarac (registered trademark) MW-30, MW-22, MW-11, MS-001 , MX-002, MX-730, MX-750, MX-035), butoxymethyl-type melamine compounds (trade names: Nikarac (registered trademark) MX-45, MX-410, MX-302), etc. are mentioned. .

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 the amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound prepared from a melamine compound and a benzoguanamine compound described in US Patent No. 6323310 can be mentioned. As a commercial item of the said melamine compound, a brand name: Cymel (trademark) 303 etc. are mentioned, As a commercial item of the said benzoguanamine compound, a brand name: Cymel (trademark) 1123 (above, Nippon Cytec Industries) Co., Ltd. (former Mitsui Cytech Co., Ltd.), etc. are mentioned.

Furthermore, as a crosslinking agent of (B) component, hydroxymethyl groups (namely, N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl methacrylamide, etc.) A polymer prepared using an acrylamide compound or a methacrylamide compound substituted with a methylol group) or an alkoxymethyl group may also be used.

Examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, A copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, etc. are mentioned. The weight average molecular weight (polystyrene conversion value) of such a polymer is 1,000-500,000, Preferably, it is 2,000-200,000, More preferably, it is 3,000-150,000, More preferably, it is 3,000-50,000.

These crosslinking agents can be used individually or in combination of 2 or more types. In addition, the polymer (specific copolymer 2) having a polymerizable group containing an N-alkoxymethyl group and a C=C double bond as a unit structure, which also serves as a crosslinking agent for component (B) and is illustrated in component (C) to be described later You can also use

It is preferable that content of the crosslinking agent of (B) component in the cured film formation composition of this invention is 1 mass part - 300 mass parts based on 100 mass parts of polymers which are (A) component, More preferably, 5 mass parts ~200 parts by mass. When content of a crosslinking agent is too little, the solvent tolerance of the cured film obtained from a cured film formation composition falls, and vertical orientation falls. On the other hand, when the content is excessive, the vertical orientation and storage stability may be deteriorated.

<(C)component>

The cured film formation composition of this invention contains either one or both of the polymer which has (C)component: adhesion promoter and (D)component mentioned later: a thermally crosslinkable group.

(C)component of this invention is a component (henceforth an adhesion improving component) which improves the adhesiveness of the cured film to be formed.

Moreover, when using the specific copolymer 2 as (B)component mentioned above so that it may mention later, (C)component may be the same as (B)component.

(C) When using the cured film formed from the cured film formation composition of this embodiment containing a component as an orientation material, the polymerizable functional group and orientation of a polymerizable liquid crystal so that the adhesiveness of an orientation material and the layer of a polymeric liquid crystal may improve. The crosslinking sites of the ashes can be linked by a covalent bond. As a result, the retardation material of this embodiment formed by laminating a cured polymerizable liquid crystal on the alignment material of this embodiment can maintain strong adhesiveness even under conditions of high temperature and high humidity, and can exhibit high durability against peeling etc. .

(C) As a component, the monomer and polymer which have group chosen from a hydroxyl group and N-alkoxy methyl group, and a polymeric group are preferable.

As such (C)component, the compound which has a hydroxyl group and a (meth)acryl group, the compound which has an N- alkoxymethyl group and a (meth)acryl group, the polymer etc. which have an N-alkoxymethyl group and a (meth)acryl group are mentioned. Specific examples are shown below, respectively.

(C) As an example of a component, the polyfunctional acrylate (henceforth a hydroxyl group containing polyfunctional acrylate) containing a hydroxyl group is mentioned.

(C) As a hydroxyl-group containing polyfunctional acrylate which is an example of a component, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. are mentioned, for example.

(C) As an example of a component, the compound which has one acryl group and one or more hydroxyl groups is also mentioned. Preferred examples of such compounds having one acrylic group and one or more hydroxyl groups are given. In addition, the compound of (C)component is not limited to the following compound examples.

[Formula 6]

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

Moreover, as a compound of (C)component, the compound which has at least 1 polymerizable group containing a C=C double bond in 1 molecule, and at least 1 N-alkoxymethyl group is mentioned.

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

N of the N-alkoxymethyl group, that is, the nitrogen atom, is a nitrogen atom of amide, a nitrogen atom of thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of urethane, and a nitrogen atom of a nitrogen-containing heterocyclic ring. A nitrogen atom etc. are mentioned. Accordingly, the N-alkoxymethyl group includes a nitrogen atom of amide, a nitrogen atom of thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of urethane, a nitrogen atom bonded to an adjacent position of a nitrogen atom of a nitrogen-containing heterocyclic ring, etc. and a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from

(C) As a component, although what is necessary is just to have said group, Preferably, the compound represented by a following formula (X1) is mentioned, for example.

[Formula 7]

(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-pene Tyl 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-pene Tyl 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-hep group Tyl 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-pene Tyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like.

Specific examples of the compound represented by the formula (X1) include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N- and acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as butoxymethyl (meth)acrylamide. In addition, (meth)acrylamide means both methacrylamide and acrylamide.

(C) As another aspect of the compound which has a polymeric group containing C=C double bond of component and N-alkoxymethyl group, Preferably, the compound represented by a following formula (X2) is mentioned, for example .

[Formula 8]

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵² and R ⁵³ each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, an aliphatic cyclic group having 5 to 6 carbon atoms, or an aliphatic group including an aliphatic ring having 5 to 6 carbon atoms in the structure, and ether It may also include bonding. 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 including an aliphatic ring having 5 to 6 carbon atoms, one of these groups is methylene or not adjacent A plurality of methylene groups may be substituted with an ether bond. Z is >NCOO- or -OCON< (where "-" represents one bond. In addition, ">" and "<" represent two bonds, and any one indicates that the alkoxymethyl group is bonded to the bonding hand). r is a natural number between 2 and 9.

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

Specific examples of the alkyl group having 2 to 20 carbon atoms include an 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 bonded to one or more of these groups within the range of up to 20 carbon atoms, and among these groups A group in which one methylene or a plurality of non-adjacent methylene groups are substituted with an ether bond is exemplified.

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, 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 definitions of R ⁵³ and R ⁵⁴ and a methyl group. Among these, a C1-C6 alkyl group is preferable, and a methyl group, an ethyl group, n-propyl group or n-butyl group is especially preferable.

Although 2 or more and 9 or less natural number are mentioned as r, 2-6 are especially preferable.

Compound (X2) is obtained by a 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 mixed with trimethylsilyl chloride and paraformaldehyde (generally, the formula (CH ₂ O) ) by reacting in a solvent to which n) is added, synthesizing an intermediate represented by the following formula (X2-2), and reacting by adding an alcohol represented by R ⁵² -OH to the reaction solution.

[Formula 9]

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 amount of trimethylsilyl chloride and paraformaldehyde used for compound (X2-1) is not particularly limited, but in order to complete the reaction, 1.0 to 6.0 equivalent times of trimethylsilyl chloride per carbamate bond in the molecule, para Formaldehyde is preferably used in an amount of 1.0 to 3.0 equivalents, and the equivalent of trimethylsilyl chloride is more preferably more than that of paraformaldehyde.

The reaction solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogen-based hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, and tetrahydrofuran; nitriles such as acetonitrile and propionitrile; nitrogen-containing polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; and pyridines such as pyridine and picoline. These solvents may be used independently, or 2 or more types of these may be mixed and used for it. Preferably they are methylene chloride and chloroform, More preferably, they are methylene chloride.

The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent, and in the case of using a solvent, 0.1 to 100 times by mass of the solvent is used with respect to compound (X2-1). may be Preferably it is 1-30 mass times, More preferably, it is 2-20 mass times.

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 may be carried out under normal pressure or under pressure, and may be batchwise or continuous.

At the time of the reaction, a polymerization inhibitor may be added. As such a polymerization inhibitor, BHT (2,6-di-tert-butyl-para-cresol), hydroquinone, para-methoxyphenol, etc. can be used, and if it inhibits polymerization of acryl group and methacryl group, it is particularly limited doesn't happen

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

In the step of reacting the intermediate (X2-2) with alcohol, a base may be added 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. Preferably they are triethylamine and diisopropylethylamine, More preferably, they are triethylamine. The amount of addition in the case of adding the base is not particularly limited, but may be used in an amount of 0.01 to 2.0 equivalents, more preferably 0.5 to 1.0 equivalents, based on the amount of trimethylsilyl chloride used in the reaction.

In addition, after obtaining the intermediate (X2-2) from the compound (X2-1), it is also possible to react by adding an alcohol without isolating the intermediate (X2-2).

The synthesis method of compound (X2-1) is not particularly limited, but by reacting (meth)acryloyloxyalkylisocyanate and a polyol compound, or by reacting a hydroxyalkyl (meth)acrylate compound with a polyisocyanate compound, can

As a specific example of (meth)acryloyloxyalkyl isocyanate, For example, 2-methacryloyloxyethyl isocyanate (Showa Denko Co., Ltd. product, brand name: Karenz MOI [registered trademark]), 2-acryl Royloxyethyl isocyanate (Showa Denko Co., Ltd. product, brand name: Karenz AOI [registered trademark]) etc. are mentioned.

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, 1, Diol compounds, such as 6-hexanediol and 1, 4- cyclohexane dimethanol, triol compounds, such as glycerol and trimethylol propane, pentaerythritol, dipentaerythritol, diglycerol, etc. are mentioned.

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, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylic The monomer etc. which have hydroxyl groups, such as a rate, are mentioned.

Specific examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimer acid diisocyanate, isophorone diisocyanate, and 4,4'-methylenebis(cyclohexyl). isocyanate), ω,ω'-diisocyanate, alicyclic diisocyanate such as dimethylcyclohexane, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1 and triisocyanates such as 3,6-hexamethylene triisocyanate and 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 a known method.

Moreover, as an example of (C)component, the polymer (henceforth specific copolymer 2) which has an N-alkoxymethyl group and the polymeric group containing a C=C double bond as a unit structure is also mentioned. As mentioned above, this can also serve as the crosslinking agent of (B)component, ie, in this case, (C)component may be the same as (B)component.

The specific copolymer is a polymer comprising a repeating unit structure comprising both groups of an N-alkoxymethyl group and a polymerizable group comprising a C=C double bond, or a repeating unit structure comprising an N-alkoxymethyl group, and C= It may be a polymer containing a repeating unit containing a polymerizable group containing a C double bond, and further, a repeating unit structure containing both groups of an N-alkoxymethyl group and a polymerizable group containing a C=C double bond, and N - It may be a polymer including a repeating unit structure of at least one of a repeating unit structure containing an 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 containing 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.

Hereinafter, the specific copolymer 2 (it is also called the polymer of (C)component) which is an example of (C)component is demonstrated.

N of the N-alkoxymethyl group, that is, the nitrogen atom, is a nitrogen atom of amide, a nitrogen atom of thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of urethane, and a nitrogen atom of a nitrogen-containing heterocyclic ring. A nitrogen atom etc. are mentioned. Accordingly, the N-alkoxymethyl group includes a nitrogen atom of amide, a nitrogen atom of thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of urethane, a nitrogen atom bonded to an adjacent position of a nitrogen atom of a nitrogen-containing heterocyclic ring, etc. and a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from

The monomer (hereinafter, also referred to as specific monomer X1) that imparts an N-alkoxymethyl group may be one having the above group, preferably, for example, a compound represented by the above formula (X1) (wherein R ² is a straight chain) or a compound representing a branched C1-C10 alkyl group).

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

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

(C) It is preferable that the specific side chain which has a polymeric group containing C=C double bond of component has 3-16 carbon atoms, and it is preferable to have an unsaturated bond at the terminal, and the specific side chain represented by following formula (b2) is Especially preferred. The specific side chain represented by the formula (b2) is bonded to the ester bond portion of the acrylic polymer, for example, as shown in the formula (b2-1).

[Formula 10]

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 a plurality of organic groups selected from this group It is an organic group consisting of a combination of R ⁴¹ may include an ester bond, an ether bond, an amide bond, or a urethane bond.

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

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

The method of obtaining the polymer which has the above specific side chains is not specifically limited.

For example, an acrylic polymer having a specific functional group (hereinafter, also referred to as a polymer having a specific functional group) is produced in advance by a polymerization method such as radical polymerization (hereinafter, the acrylic copolymer having this specific functional group is described later) As described above, an N-alkoxymethyl group has already been introduced). Next, a polymerizable group containing a C=C double bond is introduced by reacting this specific functional group with a compound having an unsaturated bond (C=C double bond) at the terminal (hereinafter referred to as a specific compound) to generate a specific side chain. And the polymer of (C)component can be obtained.

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

In the reaction for generating the specific side chain described above, a preferred combination of a specific functional group and a group involved in the reaction as a functional group (generating a characteristic side chain) of a specific compound is a carboxyl group, an epoxy group, a hydroxyl group, an isocyanate group, phenolic a hydroxyl group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxyl group and an acid chloride group. Furthermore, a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxyl group and isocyanate ethyl methacrylate.

Moreover, it is preferable that the polymer which has a specific functional group used in the reaction which produces|generates the above-mentioned specific side chain is a polymer which has an N-alkoxymethyl group and a specific functional group. That is, preferably, the polymer having a specific functional group is a functional group for reacting with a specific monomer X1, which is a monomer imparting an N-alkoxymethyl group, and a specific compound, which is a compound having an unsaturated bond (C=C double bond) at the terminal. A monomer having (a specific functional group), that is, a carboxyl group, a glycidyl group, a hydroxyl group, an amino group having an active hydrogen, a phenolic hydroxyl group or an isocyanate group (hereinafter also referred to as a specific monomer X3) is an essential component It is a copolymer obtained by making it, and it is preferable that the number average molecular weight is 2,000-25,000. Here, the monomer which has a specific functional group used for superposition|polymerization may be individual, and if it is a combination which does not react during superposition|polymerization, you may use multiple types together.

Below, the specific example of the monomer required for obtaining the polymer which has a specific functional group, ie, specific monomer X3 is 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, etc. are mentioned.

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

As a monomer which has a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxy Butyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate , caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5 -Acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone can

As a monomer which has an amino group, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned, for example.

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

As a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethylxylene isocyanate, etc. are mentioned, for example.

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

[Formula 11]

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

Moreover, in this invention, when obtaining the polymer of (C)component, it is copolymerizable with this monomer other than specific monomer X1 and specific monomer X3, The thermally crosslinkable functional group of the said (A) component (namely, a hydroxyl group) , carboxyl group, amino group, alkoxysilyl group, etc.) can be used in combination.

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

Hereinafter, specific examples of the monomer X4 are given, but the present invention is not limited thereto.

As an acrylic acid ester compound as an example of the monomer X4, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate , benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, iso Bornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-a and damantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

As a methacrylic acid ester compound as an example of the monomer X4, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate acrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2, 2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetra Hydrofurfuryl 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.

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, and 1,7-octadiene monoepoxide; and the like.

As a styrene compound which is an example of the said monomer X4, styrene, methylstyrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

As a maleimide compound which is an example of the said monomer X4, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. are mentioned, for example.

(C) It is preferable that they are 40 mol% - 90 mol% per 100 mol of all repeating units of this polymer, and, as for the abundance ratio of N-alkoxy methyl group in the polymer of component, 50 mol% - 85 mol% are still more preferable.

That is, the usage-amount of specific monomer X1 (monomer giving an N-alkoxymethyl group) used in order to obtain the specific copolymer 2 which is (C)component is the total amount of all the monomers used in order to obtain the specific copolymer 2 which is (C)component. Based on this, it is preferable that it is 40 mol% - 90 mol%, and 50 mol% - 85 mol% are more preferable.

When total is less than 40 mol%, hardening by thermal crosslinking with (A) component may become inadequate, and when exceeding 90 mol%, it may exert a bad influence on adhesiveness with a liquid-crystal layer.

(C) In the polymer of component, it is preferable that the abundance ratio of the polymeric group containing a C=C double bond is 10 mol% - 60 mol% per 100 mol of all repeating units of this polymer, 15 mol% - 50 mol % is more preferable.

That is, (C) a specific monomer X3 used to obtain a specific copolymer 2 as component (a monomer having a functional group (specific functional group) for reacting with a specific compound, which is a compound having an unsaturated bond (C=C double bond) at the terminal) Based on the total amount of all the monomers used in order to obtain the specific copolymer 2 which is (C)component, it is preferable that it is 10 mol% - 60 mol%, and, as for the usage-amount, it is more preferable that it is 15 mol% - 50 mol%.

When total is less than 10 mol%, adhesiveness with a liquid crystal layer may become inadequate, and when exceeding 60 mol%, hardening by thermal crosslinking with (A) component may become inadequate.

(C) Although the method of obtaining the specific copolymer 2 which is an example of a component is not specifically limited, For example, For example, specific monomer X1, specific monomer X3, and other monomers (for example, monomer X4) and polymerization initiator as needed. It is obtained by polymerization reaction under the temperature of 50 degreeC - 110 degreeC in the solvent which coexisted etc. At this time, the solvent used will not be specifically limited if it dissolves the said specific monomer X1, the specific monomer X3, the said other monomer used as needed, a polymerization initiator, etc. As a specific example, it describes in the term of the [solvent] mentioned later.

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

In addition, the solution of the acrylic polymer, which is an example of component (C) obtained in the above method, is added to diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed, then dried at room temperature under normal pressure or reduced pressure, or It can be heat-dried and it can be set as the powder of the specific copolymer 2 of (C)component. By the above operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer 2 of (C)component can be removed, As a result, the powder of the specific copolymer 2 which is an example of the refined (C)component is obtained lose What is necessary is just to make the obtained powder re-dissolve in a solvent again and to perform the above-mentioned operation repeatedly, when it cannot fully refine|purify by one operation.

In the composition for forming a cured film on the surface of the optical film of the present invention, the specific copolymer 2 of component (C) may be used in powder form or in the form of a solution obtained by re-dissolving purified powder in a solvent to be described later. have.

Moreover, in the composition which forms the cured film of the surface in the optical film of this invention, the specific copolymer 2 of (C)component may be multiple types of mixtures.

The weight average molecular weight of such a polymer is 1,000-500,000, Preferably, it is 2,000-200,000, More preferably, it is 3,000-150,000, More preferably, it is 3,000-50,000.

To [ content of (C)component in the cured film formation composition of embodiment of this invention / 100 mass parts of total amounts of the polymer which is (A) component, and the crosslinking agent of (B) component), Preferably it is 0.1 mass part - 100 It is a mass part, More preferably, it is 5 mass parts - 70 mass parts. (C) Adhesiveness sufficient to the cured film formed can be provided by content of a component being 0.1 mass part or more. However, when there are more than 100 mass parts, liquid-crystal orientation falls easily.

In addition, when it is the said specific copolymer 2 of (B) component, and (C)component and (B)component are the same (same compound), the compounding quantity of (C)component is grasped|ascertained as compounding quantity of (B)component (this In a case, a compounding phase shall grasp|ascertain the compounding quantity of (C)component as 0).

Moreover, the cured film formation composition of this embodiment WHEREIN: (C)component may be a mixture of multiple types of the compound of (C)component.

<(D)component>

The cured film formation composition of this invention contains any one or both of the polymer which has above-mentioned (C)component:adhesion promoter and (D)component:heat-crosslinkable group.

As the polymer (hereinafter also referred to as a specific polymer) as component (D) of the present invention, for example, acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, poly Polymers having a linear or branched structure, such as ester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkyleneimines, polyallylamines, celluloses (cellulose or derivatives thereof), phenol novolac resins, melamine formaldehyde resins, etc.; Cyclic polymers, such as cyclodextrins, etc. are mentioned.

(D) As a specific polymer which is a component, Preferably, an acrylic polymer, hydroxyalkyl cyclodextrins, celluloses, polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol are mentioned.

As an acrylic polymer, which is a preferable example of the specific polymer of component (D), a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, or a vinyl compound, and a monomer having the following specific functional group D It may be a polymer obtained by polymerizing a monomer or a mixture thereof, and is not particularly limited with respect to the backbone of the main chain of the polymer constituting the acrylic polymer, the type of side chain, and the like.

As a monomer having a specific functional group D, 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 hydroxyl group, a monomer having a carboxyl group, a monomer having an amino group, alkoxysilyl A monomer having a group, a monomer having an acetacetoxy group, and a monomer having an amide group are exemplified.

As a monomer which has the above-mentioned polyethyleneglycol ester group, the monoacrylate or monomethacrylate _of H-(OCH2CH2)p _- OH is mentioned. The value of p is 2-50, Preferably it is 2-10.

As a monomer which has the above-mentioned C2-C5 hydroxyalkyl ester group, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2- Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate are mentioned.

As a monomer which has the above-mentioned phenolic hydroxyl group, p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene are mentioned, for example.

As a monomer which has the above-mentioned carboxyl group, acrylic acid, methacrylic acid, and vinylbenzoic acid are mentioned, for example.

As a monomer which has the above-mentioned amino group in a side chain, 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate are mentioned, for example.

Examples of the monomer having the above-described alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-meth Cryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, etc. are mentioned.

As a monomer which has the above-mentioned acetacetoxy group in a side chain, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, etc. are mentioned, for example.

In addition, in this embodiment, in synthesizing the acrylic polymer which is an example of (D)component, unless the effect of this invention is impaired, the monomer which does not have the specific functional group D mentioned above, for example, a hydroxyl group, a carboxyl group, A monomer having neither an amide group, an amino group, an alkoxysilyl group nor an acetacetoxy group can be used in combination.

As a specific example of such a monomer, an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylonitrile, maleic anhydride, a styrene compound, a vinyl compound, etc. are mentioned.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl 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-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , and 8-ethyl-8-tricyclodecyl acrylate.

As a methacrylic acid ester compound, For example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate Rate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methacrylate Toxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl -2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc. are mentioned.

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

As a styrene compound, styrene, methyl styrene, chloro styrene, bromostyrene etc. are mentioned, for example.

Examples of the vinyl compound 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 a specific functional group D used to obtain the acrylic polymer as an example of component (D) is 2 mol% to 98 mol% based on the total amount of all monomers used to obtain the acrylic polymer as component (D) desirable. When there is too little the monomer which has specific functional group D, the liquid-crystal orientation of the cured film obtained becomes inadequate easily, and when too much, compatibility with (A) component falls easily.

(D) The method for obtaining the acrylic polymer as an example of the component is not particularly limited, for example, a monomer containing a monomer having a specific functional group D, a monomer having no specific functional group D if necessary, a polymerization initiator, etc. coexist In the prepared solvent, it is obtained by polymerization at a temperature of 50°C to 110°C. At this time, the solvent to be used is not particularly limited as long as it dissolves a monomer having a specific functional group D, a monomer not having a specific functional group D used as necessary, a polymerization initiator, and the like. As a specific example, it describes in the term of the [solvent] mentioned later.

The acrylic polymer which is an example of (D)component obtained by the above method is the state of the solution melt|dissolved in the solvent normally.

In addition, the solution of the acrylic polymer as an example of component (D) obtained by the above method is added to diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed, then dried at room temperature under normal pressure or reduced pressure, or It can be heat-dried and it can be set as the powder of the acrylic polymer which is an example of (D)component. By the above operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer which is an example of (D)component can be removed, As a result, the powder of the acrylic polymer which is an example of the refined (B) component is obtained. What is necessary is just to make the obtained powder re-dissolve in a solvent again and to perform the above-mentioned operation repeatedly, when it cannot fully refine|purify by one operation.

(D) It is preferable that weight average molecular weights are 3,000-200,000, as for the acrylic polymer which is a preferable example of a component, it is more preferable that it is 4,000-150,000, It is still more preferable that it is 5,000-100,000. If the weight average molecular weight exceeds 200,000 and is excessive, solubility in solvents may decrease and handleability may decrease. Heat resistance may fall. In addition, the weight average molecular weight is a value obtained using polystyrene as a standard sample by gel permeation chromatography (GPC). Hereinafter, it is assumed that it is the same also in this specification.

Next, as polyether polyol which is a preferable example of the specific polymer of (D)component, propylene oxide, polyethyleneglycol, polypropylene to polyhydric alcohol, such as polyethyleneglycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, and sorbitol. What added glycol etc. is mentioned. Specific examples of polyether polyols include ADEKA Co., Ltd. Adeka polyether P series, G series, EDP series, BPX series, FC series, CM series, Nichiyu Co., Ltd. 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.

(D) As a polyester polyol which is a preferable example of the specific polymer of a component, polyhydric carboxylic acids, such as adipic acid, sebacic acid, isophthalic acid, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc. What made diol react is mentioned. Specific examples of the polyester polyol include DIC Corporation Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD -X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X -2523, OD-X-2555, OD-X-2560, Kurarese Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F -510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc. are mentioned.

(D) As a polycaprolactone polyol which is a preferable example of the specific polymer of component, what carried out ring-opening polymerization of epsilon caprolactone using polyhydric alcohols, such as trimethylol propane and ethylene glycol, as an initiator is mentioned. Specific examples of polycaprolactone polyol include DIC Corporation Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Co., Ltd. Fraxel (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc. are mentioned.

(D) As a polycarbonate polyol which is a preferable example of the specific polymer of component, what made polyhydric alcohol, such as trimethylol propane and ethylene glycol, and diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. react is mentioned. Specific examples of the polycarbonate polyol include Daicel Co., Ltd. Fraxel (registered trademark) CD205, CD205PL, CD210, CD220, Kurare Co., Ltd. C-590, C-1050, C-2050, C-2090, C- 3090 etc. are mentioned.

(D) As a cellulose which is a preferable example of the specific polymer of a component, hydroxyalkyl celluloses, such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylethylcellulose, etc. of hydroxyalkylalkyl celluloses and cellulose, and for example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

(D) As a cyclodextrin which is a preferable example of the specific polymer of component, Cyclodextrins, such as alpha-cyclodextrin, beta-cyclodextrin, and gamma cyclodextrin, methyl-alpha-cyclodextrin, methyl- beta-cyclodextrin, and methyl- Methylated cyclodextrin such as γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2- Hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ- Cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, Hydroxyalkyl cyclodextrins, such as 2, 3- dihydroxypropyl-(beta)-cyclodextrin and 2, 3- dihydroxypropyl-(gamma)-cyclodextrin, etc. are mentioned.

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

[Formula 12]

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.

As for the melamine formaldehyde resin of (D)component, it is preferable that the methylol group produced|generated at the time of polycondensation of melamine and formaldehyde from a viewpoint of storage stability is alkylated.

(D) The method for obtaining the melamine formaldehyde resin of component is not particularly limited, but generally, melamine and formaldehyde are mixed, and then made weakly alkaline using sodium carbonate or ammonia, etc., and then synthesized by heating at 60°C to 100°C do. Furthermore, a methylol group can be alkoxylated by making it react with alcohol.

(D) It is preferable that weight average molecular weights are 250-5,000, as for the melamine formaldehyde resin of component, it is more preferable that it is 300-4,000, It is more preferable that it is 350-3,500. If the weight average molecular weight exceeds 5,000 and is excessive, solubility in solvents may decrease and handleability may decrease. The effect of improving the heat resistance may not be sufficiently exhibited.

In embodiment of this invention, the melamine formaldehyde resin of (D)component is a liquid form, or you can also use it with the solution form which melt|dissolved the refined liquid again in the solvent mentioned later.

(D) As a phenol novolak resin which is a preferable example of the specific polymer of component, a phenol-formaldehyde polycondensate etc. are mentioned, for example.

Cured film formation composition of this embodiment WHEREIN: The polymer of (D)component is a powder form, or can also use it with the solution form which melt|dissolved the refined powder again in the solvent mentioned later.

Preferably content of (D)component in the cured film formation composition of this invention is 400 mass parts or less with respect to 100 mass parts of total amounts of the polymer which is (A) component, and the crosslinking agent of (B)component, More preferably is 10 parts by mass to 380 parts by mass, more preferably 40 parts by mass to 360 parts by mass. (D) When content of component is excessive, liquid-crystal orientation falls easily, and when too little, adhesiveness falls easily.

In addition, the cured film formation composition of this embodiment WHEREIN: (D)component may be a mixture of multiple types of polymers illustrated as (D)component.

<(E) component>

In addition to the said (A) component, (B) component, (C)component, and/or (D)component, the cured film formation composition of this invention can contain a crosslinking catalyst as (E)component further.

(E) As a crosslinking catalyst which is a component, an acid or a thermal acid generator can be used suitably, for example. When this (E)component accelerates|stimulates the thermosetting reaction of the cured film formation composition of this invention, it is effective.

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

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

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

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

and the like.

To [ content of (E) component in the cured film formation composition of this invention / 100 mass parts of total amounts of the polymer which is (A) component, and the crosslinking agent of (B) component), Preferably 0.01 mass part - 20 mass parts, More preferably, they are 0.1 mass part - 15 mass parts, More preferably, they are 0.5 mass part - 10 mass parts. (E) Sufficient thermosetting and solvent tolerance can be provided by content of a component being 0.01 mass part or more. However, when more than 20 mass parts, the storage stability of a composition may fall.

<solvent>

The cured film formation composition of this invention is mainly used in the solution state melt|dissolved in the solvent. The solvent used at this time, (A) component, (B) component, (C) component and / or (D) component, if necessary, (E) component and / or other additives to be described later if necessary , its type and structure are not particularly limited.

Specific examples of the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone Non, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionate ethyl, ethoxyethyl acetate, ethyl hydroxyacetate, 2-hydroxy Methyl -3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate , butyl lactate, cyclopentylmethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

When using the cured film forming composition of the present invention to form a cured film on a resin film to prepare an orientation material, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2 -Heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. are preferable at the point that a resin film is a solvent which shows resistance.

These solvents can be used individually by 1 type or in combination of 2 or more types.

<Other additives>

Furthermore, the cured film-forming composition of the present invention, if necessary, as long as the effects of the present invention are not impaired, an adhesion enhancer, a silane coupling agent, a surfactant, a rheology adjuster, a pigment, a dye, a storage stabilizer, an antifoaming agent, an antioxidant and the like.

<Preparation of a cured film forming composition>

The cured film formation composition of this invention contains the polymer which has the polymer of (A) component, the crosslinking agent of (B) component, the adhesion promoter of (C) component, and/or the thermally crosslinkable group of (D) component, If necessary, Accordingly, it is a composition which can contain the crosslinking catalyst of component (E) and other additives as long as the effect of this invention is not impaired further. And usually, these are used as the form of the solution which melt|dissolved in the solvent.

The preferable example of the cured film formation composition of this invention is as follows.

[1]: Based on 100 mass parts of (A) component and (A) component, 1 mass part - 300 mass parts (B) component, and the polymer which is (A) component, and the total amount of the crosslinking agent of (B) component 100 The cured film formation composition containing at least one of 0.1 mass parts - 100 mass parts (C)component and 1 mass parts - 400 mass parts (D)component with respect to mass parts.

[2]: Based on 100 mass parts of (A) component and (A) component, 1 mass part - 300 mass parts (B) component, the polymer which is (A) component, and 100 mass parts of total amounts of the crosslinking agent of (B) component The cured film formation composition containing 0.1 mass parts - 100 mass parts (C)component, and at least one of 1 mass parts - 400 mass parts (D)component with respect to, and a solvent.

[3]: Based on 100 mass parts of (A) component and (A) component, 1 mass part - 300 mass parts (B) component, the polymer which is (A) component, and 100 mass parts of total amounts of the crosslinking agent of (B) component 0.01 to 100 parts by mass of the total amount of the crosslinking agent of 0.1 parts by mass to 100 parts by mass of (C) component and 1 part by mass to 400 parts by mass of (D) component, the polymer which is (A) component, and (B) component The cured film formation composition containing (E) component and a solvent in mass - 20 mass parts.

[4]: Based on 100 mass parts of (A) component and (A) component, 1 mass part - 300 mass parts (B) component, the polymer which is (A) component, and 100 mass parts of total amounts of the crosslinking agent of (B) component With respect to 0.1 mass parts - 100 mass parts with respect to (C)component, 1-400 mass parts with respect to 100 mass parts of the total amount of the polymer which is (A) component, and the crosslinking agent of (B) component, (D)component, the polymer which is (A) component And the cured film formation composition containing 0.01 mass parts - 20 mass parts (E) component, and a solvent with respect to 100 mass parts of total amounts of the crosslinking agent of (B) component.

The compounding ratio in the case of using the cured film formation composition of this invention as a solution, a preparation method, etc. are demonstrated in detail below.

Although the ratio of solid content in the cured film formation composition of this invention is not specifically limited as long as each component is melt|dissolving in the solvent uniformly, It is 1 mass % - 60 mass %, Preferably they are 2 mass % - 50 mass %, and more preferably 2% by mass to 20% by mass. Here, solid content means what removed the solvent from all the components of a cured film formation composition.

The preparation method of the cured film formation composition of this invention is not specifically limited. As a preparation method, for example, (B) component, (C)component and/or (D)component, further (E)component etc. are mixed in the solution of (A) component dissolved in a solvent in a predetermined ratio, , a method of making a uniform solution, or a method of adding and mixing other additives as needed in an appropriate step of the preparation method.

In preparation of the cured film formation composition of this invention, the solution of the specific copolymer (polymer) obtained by the polymerization reaction in a solvent can be used as it is. In this case, for example, (B)component, (C)component, (D)component, further (E)component etc. are put into the solution of (A)component similarly to the above, and it is set as a uniform solution. At this time, the solvent may be additionally added again for the purpose of concentration adjustment. At this time, the solvent used in the production|generation process of (A) component and the solvent used for density|concentration adjustment of a cured film formation composition may be the same, and may differ.

Moreover, it is preferable to use, after filtering the solution of the prepared cured film formation composition using the filter etc. whose pore diameter is about 0.2 micrometer.

<Cured film, alignment material and phase difference material>

A solution of the cured film forming composition of the present invention is applied to a substrate (also referred to as a substrate) (for example, a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc.; Glass substrate, quartz substrate, ITO substrate, etc.) or film substrate (eg, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, Polyethylene terephthalate (PET) film, acrylic film, resin film such as polyethylene film), etc., by bar coating, rotational application, drip application, roll application, slit application, rotational application following the slit, inkjet application, printing, etc. A cured film can be formed by apply|coating, forming a coating film, and heating-drying with a hotplate or oven after that. This cured film can be applied as an orientation material as it is.

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

The film thickness of the cured film (orientation material) formed using the curable composition of this invention is 0.05 micrometer - 5 micrometers, for example, Considering the level|step difference of the board|substrate to be used, and optical and electrical properties, it can select suitably.

Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical alignment property may be applied on the alignment material and aligned on the alignment material. And by hardening the retardation material which became an orientation state as it is, the retardation material can be formed as a layer which has optical anisotropy. And when the board|substrate which forms an orientation material is a film, it becomes useful as retardation film.

In addition, using two substrates having the alignment material of the present invention formed as described above, and bonding the alignment materials on both substrates to face each other through a spacer, liquid crystal is injected between these substrates to align the liquid crystal It can also be set as a liquid crystal display device.

Thus, the cured film formation composition of this invention can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.

[Example]

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

[Abbreviations used in the examples]

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

<Ingredients of each ingredient>

jER-1001: Mitsubishi Chemical Co., Ltd. bisphenol A type epoxy resin molecular weight 900

jER-1055: Mitsubishi Chemical Co., Ltd. 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: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of trimethylolpropane manufactured by Daicel Co., Ltd.

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 crosslinking agent represented by the following structural formula [CYMEL (registered trademark) 303 (manufactured by Mitsui Cytec)]

[Formula 19]

<(C)component>

BMAA: N-butoxymethylacrylamide

DM-1:

[Formula 20]

<(D)component>

PUA: Polyurethane graft acrylic polymer [Acrit (registered trademark) 8UA-146 (manufactured by Osaka 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.)

[Formula 21]

(In the 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: cyclopentylmethyl ether

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

<(A) synthesis of component> (1)

<Synthesis Example 1>

50.0 g of jER-1001, 6.25 g of LAUA, and 0.14 g of BTEAC were dissolved in 131.58 g of PM and reacted at 110°C for 16 hours to obtain a vertical alignment polymer (solid content concentration of 30% by mass) (PA1). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the amount of epoxy groups in which LAUA reacted completely disappeared.

<Synthesis Example 2>

50.0 g of jER-1055, 3.54 g of LAUA, and 0.079 g of BTEAC were dissolved in 125.0 g of PM and reacted at 110° C. for 16 hours to obtain a vertical alignment polymer (solid content concentration: 30 mass%) (PA2). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the amount of epoxy groups in which LAUA reacted completely disappeared.

<Synthesis Example 3>

50.0 g of jER-157S70, 14.3 g of LAUA, and 0.33 g of BTEAC were dissolved in 150.8 g of PM, and reacted at 110°C for 16 hours to obtain a vertical alignment polymer (solid content concentration: 30% by mass) (PA3). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the amount of epoxy groups in which LAUA reacted completely disappeared.

<Synthesis Example 4>

50.0 g of ECN-1299, 14.0 g of LAUA, and 0.32 g of BTEAC were dissolved in 150.2 g of PM and reacted at 110° C. for 16 hours to obtain a vertical alignment polymer (solid content concentration of 30 mass%) (PA4). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the amount of epoxy groups in which LAUA reacted completely disappeared.

<Synthesis Example 5>

50.0 g of EHPE-3150, 5.59 g of LAUA, and 0.036 g of BTEAC were dissolved in 129.8 g of PM and reacted at 110° C. for 16 hours to obtain a vertical alignment polymer (solid content concentration of 30 mass%) (PA5). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the amount of epoxy groups in which LAUA reacted completely disappeared.

<Synthesis Example 6>

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

<(B) synthesis of component> (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). Mn of the obtained acrylic copolymer was 4,800, and Mw was 3,100.

<(C)Synthesis of component>

<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, filtered and dried under reduced pressure to obtain an acrylic copolymer (PC1). Mn of the obtained acrylic copolymer was 7,000, and Mw was 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, and 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM, followed by reaction at 90° C. for 20 hours. This solution was gradually dripped at 500 g of hexane, solid was precipitated, and the acrylic copolymer (PC2) which has an acroyl group was obtained by filtering and drying under reduced pressure. ¹ H-NMR analysis was performed to confirm that the acrylic copolymer (PC2) had an acroyl group.

Moreover, PC2 acts also as (B) component in this invention.

Synthesis of compound [DM-1]

[Formula 22]

In a nitrogen stream, 500 g of ethyl acetate, 35.5 g (0.300 mol) of 1,6-hexanediol, 1.80 g of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) in a 2L four-necked flask ( 11.8 mmol), 2,6-di-tertbutyl-para-cresol (BHT) 0.45 g (2.04 mmol) was added at room temperature, and the temperature was raised to 55° C. under stirring with a magnetic stirrer. 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 reaction was performed when the intermediate was 1% or less in area percentage. has been completed 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%).

[Formula 23]

In a nitrogen stream, 1330 g of dichloromethane, 100 g (0.250 mol) of compound [Aa], and 22.5 g (0.749 mol) of paraformaldehyde were put into a 2L four-necked flask, and 122 g (1.12 mol) of trimethylsilyl chloride was added dropwise in an ice bath. did After stirring for 2 hours, a mixture of 63.2 g (0.625 mol) of triethylamine and 240 g of methanol was added dropwise. After stirring for 30 minutes, it was transferred to a 5 L separatory funnel, and 1500 g of water was added to perform a liquid separation operation. The obtained organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the resulting filtrate was concentrated and dried to obtain compound [DM-1] (110 g, 0.226 mol, yield 90.3%). The structure of compound [DM-1] was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ6.42 (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).

<(D)Synthesis of component>

<Synthesis Example 10>

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

<(A) synthesis of component> (2)

<Synthesis Example 11>

EHPE-3150 44.2g, LAUA 15.4g, BTEAC 0.44g was melt|dissolved in PM 240.0g, and made to react at 110 degreeC for 16 hours, The vertical orientation polymer (solid content concentration 20 mass %) (PA7) was obtained. The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the amount of epoxy groups in which LAUA reacted completely disappeared.

<Synthesis Example 12>

EHPE-3150 40.1 g, 5CCA 19.5 g, and BTEAC 0.40 g were dissolved in 240.0 g PM, and reacted at 110° C. for 16 hours to obtain a vertical alignment polymer (solid content concentration: 20 mass%) (PA8). The epoxy value of the obtained vertically oriented polymer was measured, and it was confirmed that the amount of epoxy groups in which A5 was completely reacted disappeared.

<(B) synthesis of component> (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). Mn of the obtained acrylic copolymer was 2,700, and Mw was 3,900.

<Preparation of base film>

The acrylic film used as a base material can be created by the following method, for example. That is, raw material pellets made of a copolymer containing methyl methacrylate as a main component are melted at 250° C. by an extruder, passed through a T-die, and an acrylic film having a thickness of 40 μm can be prepared through casting rolls and drying rolls.

<Examples, Comparative Examples>

Each cured film formation composition of an Example and a comparative example was prepared with the composition shown in Table 1. In addition, all the compounding quantities of (A) - (E) component in Table 1 are solid content conversion (when obtained as a solution at the time of preparation, a solvent is removed). Next, the cured film was formed using each phase difference re-formation composition, and vertical orientation and adhesive evaluation were performed about each obtained cured film.

[Table 1]

[Evaluation of vertical orientation]

<Examples 1 to 18, Comparative Examples 1 to 4>

On the base material shown in Table 2 or Table 3, each cured film formation composition of Examples 1-18 and Comparative Examples 1-4 was apply|coated with the wet film thickness of 4 micrometers using the bar coater. Then, heat-drying was performed at the temperature of 110 degreeC for 60 second in each heat-circulation type oven, respectively, and the cured film was respectively formed on each base material.

On this cured film, Merck Corporation's polymerizable liquid crystal solution RMS03-015 for vertical alignment was applied with a wet film thickness of 6 µm using a bar coater. The coating film on this base material was exposed at 600 mJ/cm< ² >, and the retardation material was produced.

The incident angle dependence of the in-plane retardation was measured for these produced retardation materials using a retardation measuring apparatus RETS100 manufactured by Otsuka Electronics Co., Ltd. When the in-plane retardation value at the incident angle of 0° was 0 and the in-plane retardation at the incident angle of ±50° was in the range of 38±5 nm, it was judged that the vertical alignment was performed. The evaluation results of Examples 1 to 15 and Comparative Examples 1 and 2 are referred to as "vertical orientation" in Table 2, and the evaluation results of Examples 16 to 18 and Comparative Examples 3 to 4 are shown in Table 3.

[Evaluation of adhesion]

<Examples 1-15, Comparative Examples 1-2>

On the base material shown in Table 2, each cured film formation composition of an Example and a comparative example was apply|coated with the wet film thickness of 4 micrometers using the bar coater. Then, heat-drying was performed in the heat circulation type oven for 60 second at the temperature of 110 degreeC, respectively, respectively, and the cured film was formed on the base material, respectively.

On this cured film, Merck Corporation's polymerizable liquid crystal solution RMS03-015 for vertical alignment was applied with a wet film thickness of 6 µm using a bar coater. The coating film on this base material was exposed at 600 mJ/cm< ² >, and the retardation material was produced.

The phase difference material was cut with a cutter knife so that it was 5 × 5 squares at intervals of 1 mm in width and length. A cellophane tape peeling test was performed on this sheath using a scotch tape. In evaluation, the thing which remained without peeling all 25 squares was made into (circle) and the thing which peeled even 1 square was made into *. An evaluation result is summarized and shown in Table 2 by "adhesion property" later.

[Table 2]

[Table 3]

As shown in Table 2, the orientation material obtained using the cured film formation composition of Examples 1-15 showed favorable vertical orientation similarly to the orientation material obtained using the cured film formation composition of Comparative Examples 1-2. Moreover, as shown in Table 3, the orientation material obtained using the cured film formation composition of Examples 16-18 is compared with the orientation material obtained using the cured film formation composition of Comparative Examples 3 and 4, In various base materials, It showed good vertical orientation.

Moreover, the cured film obtained using the cured film formation composition of Examples 1-15 showed the outstanding adhesiveness. On the other hand, it was difficult for the cured film obtained using the cured film formation composition of Comparative Examples 1-2 to acquire 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 a liquid crystal display device, in particular, IPS- It is suitable as a material for optical compensation film of LCD.

Claims (10)

(A) a polymer in which the carboxyl group of the compound in which the carboxyl group is bonded to the vertical orientation group is reacted with the epoxy group of the polymer having one or more epoxy groups in the side chain or at the terminal;
(B) a crosslinking agent having a methylol group or an alkoxymethyl group, and
(C) any one or both of a group selected from a hydroxyl group and an N-alkoxymethyl group, an adhesion promoter selected from monomers and polymers having a polymerizable group, and (D) a polymer having a thermally crosslinkable group
As a cured film forming composition containing,
The vertical alignment group is an alkyl group having 6 to 20 carbon atoms, or a group represented by the following formula [1], the cured film forming composition.

(in formula [1],
* indicates a bonding position,
Y ¹ To Y ⁴ Represent a single bond,
Y ⁵ represents a divalent cyclic group selected from a benzene ring and a cyclohexane ring,
n represents an integer of 2 to 3, and when n is 2 or more, Y ⁵ may be the same or different,
Y ⁶ represents an alkyl group having 1 to 18 carbon atoms.
However, in the definition of Formula [1],
A polymer having a methylol group or an alkoxymethyl group shall be (B) component,
A monomer and a polymer having a group selected from a hydroxyl group and an N-alkoxymethyl group and a polymerizable group shall be the component (C)).
The method of claim 1,
The cured film forming composition, wherein the polymer having one or more epoxy groups in the side chain or the terminal is a polymer having a number average molecular weight of 300 to 20,000 having a ring structure in the main chain.
The method of claim 1,
The polymer having at least one epoxy group in the side chain or terminal is one of bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, and polyol The cured film forming composition which is any 1 type of polymer selected from the group which consists of ,2-epoxy-4- (2-oxiranyl) cyclohexane adduct.
delete The method of claim 1,
(E) The cured film formation composition which further contains a crosslinking catalyst.
The method of claim 1,
(A) The cured film formation composition containing 1 mass part - 300 mass parts (B) component based on 100 mass parts of components.
The method of claim 1,
(A) Contains any one or both of 0.1 mass parts - 100 mass parts (C)component and 1 mass part - 400 mass parts (D)component with respect to 100 mass parts of total amounts of the crosslinking agent of the polymer which is a component and (B) component which is a cured film forming composition.
6. The method of claim 5,
(A) The cured film formation composition containing 0.01 mass parts - 20 mass parts (E) component with respect to 100 mass parts of total amounts of the crosslinking agent of the polymer and (B) component which is a component.
It is obtained by hardening|curing the cured film formation composition in any one of Claims 1-3 and 5-8, The orientation material characterized by the above-mentioned.
It is formed using the cured film obtained from the cured film formation composition in any one of Claims 1-3 and 5-8, The retardation material characterized by the above-mentioned.