TWI843698B - Cured film formation composition, orientation material and retardation material - Google Patents

Abstract

The subject of the present invention is to provide an alignment material having excellent vertical alignment and capable of vertically aligning polymerizable liquid crystals with high sensitivity even on a resin film, and a cured film forming composition for a phase difference material using such an alignment material. 　　The means for solving the problem are the cured film forming composition, the alignment material, and the phase difference material of the present invention, wherein the cured film forming composition contains the following components: (A) a polymer having a vertical alignment group, (B) a compound having two or more polymerizable groups containing a C=C double bond, and (C) a free radical polymerization initiator, wherein the characteristic is that substantially only the component (B) has a polymerizable group containing a C=C double bond.

Description

Cured film forming composition, alignment material and phase difference material

The present invention relates to a cured film forming composition, which is a vertical alignment material suitable for aligning liquid crystal molecules vertically. In particular, the present invention relates to a cured film forming composition, an alignment material, and a phase difference material useful for making a +C plate (positive-C plate) used to improve the viewing angle characteristics of a liquid crystal display (LCD) such as an IPS liquid crystal display (In-plane Switching LCD) filled with a liquid crystal having positive dielectric anisotropy (△ε＞0), or to improve the viewing angle characteristics of a circular polarizer used as an anti-reflection film for an organic EL display.

Since IPS-LCD does not produce vertical tilt of liquid crystal molecules, its characteristic is that the brightness change/color change caused by the viewing angle is small, but its weaknesses include difficulty in improving the contrast ratio, brightness, response speed, etc. For example, as disclosed in Patent Document 1, the IPS-LCD proposed in the early stage did not use a viewing angle compensation film. Such IPS-LCD without a viewing angle compensation film has a disadvantage of showing a low contrast ratio value due to relatively large light leakage in the dark state at a tilt angle.

Patent document 2 discloses an IPS-LCD compensation film using a +C plate and a +A plate (positive A plate). In this document, the liquid crystal display element described therein has the following structure. 1) A liquid crystal layer with a horizontal orientation is sandwiched between two substrates supplied by electrodes that can apply an electric field parallel to the liquid crystal layer. 2) One or more +A plates and +C plates are sandwiched by two polarizing plates. 3) The main optical axis of the +A plate is perpendicular to the main optical axis of the liquid crystal layer. 4) Confirm 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 so that they satisfy the following formula. R _LC : R _+C : R _+A ≒1:0.5:0.25 5) The relationship between the retardation value of the +A plate and the +C plate in the thickness direction of the protective film of the polarizing plate (TAC, COP, PNB) is not shown.

In addition, an IPS-LCD having a +A plate and a +C plate is disclosed, the purpose of which is to provide an IPS-LCD having high contrast ratio characteristics and low color shift at the front and tilt angles by minimizing light leakage in the dark state at a tilt angle (Patent Document 3). Furthermore, a circular polarizing plate for improving the viewing angle characteristics of a circular polarizing plate is also proposed, and the circular polarizing plate is a circular polarizing plate that uses the +C plate as an anti-reflection film for an organic EL display (Patent Document 5). [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2-256023 [Patent Document 2] Japanese Patent Publication No. 11-133408 [Patent Document 3] Japanese Patent Publication No. 2009-122715 [Patent Document 4] Japanese Patent Publication No. 2001-281669 [Patent Document 5] Japanese Patent Publication No. 2015-79256

[The problem that the invention wants to solve]

As proposed in the past, since the +C plate can compensate for light leakage in places where the viewing angle of the polarizing plate is large, it is very useful as an optical compensation film for circular polarizing plates used as anti-reflection films for IPS-LCD or organic EL displays. However, it is difficult to make it exhibit vertical alignment (positive C plate) properties by the conventionally known stretching treatment method.

In addition, the vertical alignment film using polyimide that has been proposed in the past requires the use of a solvent of polyimide such as N-methyl-2-pyrrolidone when the film is produced. Therefore, there is no problem for a glass substrate, but if the substrate is a thin film, there will be problems such as damage to the substrate when the alignment film is formed. Moreover, the vertical alignment film using polyimide requires sintering at a high temperature, and there is a problem that the thin film substrate cannot withstand high temperatures. 　　Furthermore, a method of forming a vertical alignment film by directly treating the substrate with a silane coupling agent having a long-chain alkyl group has also been proposed, but when there is no hydroxyl group on the surface of the substrate, there will be problems such as difficulty in processing and restrictions on the substrate (Patent Document 4).

In recent years, in response to the demand for reducing manufacturing costs, it has been required to produce +C plates on cheap resin films such as TAC (triacetyl cellulose) films and COP (cycloolefin polymer) films by so-called roll-to-roll production. However, it is difficult to produce +C plates on resin films with alignment films formed from conventional materials such as those mentioned above.

Therefore, there is a demand for an alignment material that can form a highly reliable +C plate even on a resin film such as a TAC film, and a cured film forming composition for forming such an alignment material.

The present invention is completed based on the above insights or research results, and the problem to be solved is to provide a hardened film-forming composition for providing an alignment material, wherein the alignment material has excellent vertical alignment and at the same time has the transparency or solvent resistance required for an optical compensation film, and even on a resin film, it can utilize low-temperature and short-time sintering conditions to stably align polymerizable liquid crystals vertically.

In addition, another object of the present invention is to provide an alignment material and a phase difference material useful for a +C plate formed using the alignment material. The alignment material is obtained from the above-mentioned cured film forming composition, has excellent vertical alignment, is resistant to solvents, and can stably align polymerizable liquid crystals vertically even on a resin film under low-temperature and short-time sintering conditions. 　　Other objects and advantages of the present invention are indicated by the following description. 　　 [Means for Solving the Problem]

The inventors of the present invention have conducted intensive studies to achieve the above-mentioned purpose and have found that by selecting a cured film forming material composed of a polymer having a vertical alignment group and a compound having two or more polymerizable groups containing a C=C double bond as a matrix, a cured film having excellent vertical alignment can be formed, thereby completing the present invention.

That is, the first aspect of the present invention is a cured film forming composition comprising the following components: (A) a polymer having a group represented by the following formula [1] as a vertical alignment group, (B) a compound having two or more polymerizable groups containing a C=C double bond, and (C) a radical polymerization initiator, wherein substantially only component (B) has a polymerizable group containing a C=C double bond. (In formula [1], ^Y1 represents a single bond, or a bonding group selected from the group consisting of -O-, _-CH2O- , -COO-, -OCO-, -NHCO-, -NH-CO-O-, and -NH-CO-NH-; ^Y2 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms (the alkylene group may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other) or _-CH2- CH(OH) _-CH2 -, or represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring (the divalent cyclic group is a cyclic group in which any hydrogen atom may be substituted by a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy 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 (the alkylene group may be any of a linear, branched or cyclic group, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other); Y ^Y represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring (the divalent cyclic group is a cyclic group in which any hydrogen atom may be substituted by a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom), or a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton; ^Y5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring (the divalent cyclic group is a cyclic group in which any hydrogen atom may be substituted by a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom); n represents an integer of 0 to 4. If n is 2 or more, the respective ^Y5s may be the same or different; Y wherein ^{Y2 and Y3} represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorinated alkoxy group having 1 to 18 carbon atoms (the alkyl group having 1 to 18 carbon atoms, the fluorinated alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, and the fluorinated alkoxy group having 1 to 18 carbon atoms may be in a linear, branched, or cyclic form, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other); when ^Y2 and ^Y3 represent a group other than a single bond, the bond between ^Y2 and ^Y3 may be a single bond or may be via a bonding group A; when ^Y3 and ^Y4 represent a group other than a single bond, ^Y3 and Y4 may be in a linear, branched, or cyclic form, or a combination thereof. The bond between ^Y4 and ^{Y5 may be a single bond or may be via a bonding group A. When Y4 and Y5 represent} groups other than single bonds, the bond between ^Y4 and ^Y5 may be a single bond or may be via a bonding group A. When ^Y5 and ^Y6 represent groups other than single bonds, the bond between ^Y5 and ^Y6 may be a single bond or may be via a bonding group A. When n is 2 or more, the bond between one ^Y5 and the adjacent ^Y5 may be a single bond or may be via a bonding group A. The bonding group A represents a group selected from the group consisting of -O-, _-CH2O- , -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH-. However, the total number of carbon atoms contained in the group represented by formula [1] is 6 to 30).

As a second aspect, it is related to the cured film forming composition as described in the first aspect, wherein the polymerizable group containing a C=C double bond of the component (B) is at least one selected from an acrylic group, a methacrylic group, a vinyl group, an allyl group and a maleimide group. 　　As a third aspect, it is related to the cured film forming composition as described in the first aspect or the second aspect, wherein the component (B) is contained in an amount of 10 parts by mass to 2000 parts by mass based on 100 parts by mass of the component (A). 　　As a fourth aspect, it is related to the cured film forming composition as described in any one of the first to third aspects, wherein the component (C) is contained in an amount of 0.1 parts by mass to 50 parts by mass per 100 parts by mass of the component (A).

As a fifth aspect, it is about an orientation material, which is characterized in that it is obtained by curing a cured film forming composition as described in any one of the first to fourth aspects. 　　As a sixth aspect, it is about a phase difference material, which is characterized in that it is formed using a cured film obtained from a cured film forming composition as described in any one of the first to fourth aspects. 　　 [Effect of the Invention]

According to the first aspect of the present invention, a curing film forming composition useful for providing an alignment material can be provided, wherein the alignment material has excellent vertical alignment and can stably align polymerizable liquid crystals vertically even on a resin film by using low-temperature, short-time firing conditions. 　　According to the second aspect of the present invention, an alignment material can be provided that has excellent vertical alignment and can stably align polymerizable liquid crystals vertically by using low-temperature, short-time firing conditions. 　　According to the third aspect of the present invention, a phase difference material can be provided that can be efficiently formed even on a resin film and that is highly transparent and highly solvent-resistant.

[Best Mode for Carrying Out the Invention]

<Curing film forming composition> 　　The curing film forming composition of the present invention is characterized by containing the following components: 　　A polymer having a vertically oriented group as component (A), a compound having two or more polymerizable groups containing a C=C double bond as component (B), and a free radical polymerization initiator as component (C), wherein substantially only component (B) has a polymerizable group containing a C=C double bond. In addition, other additives may be contained as long as the effects of the present invention are not impaired. 　　The following describes the details of each component.

＜Component (A)＞ The component (A) contained in the cured film forming composition of the present invention is a polymer having a vertically oriented group.

More specifically, the vertical alignment group is a group represented by the following formula [1]. In formula [1], Y 2 represents a single bond or a bonding group selected from the group consisting of -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH-. In formula [1], Y ² represents a single bond or a linear or branched alkylene group having 1 to 15 carbon atoms, and the alkylene group may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other. As Y ² , -CH ₂ -CH(OH)-CH ₂ - can also be cited. Also, Y ² may be a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted with a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

Examples of the heterocyclic ring 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 thiazolidine ... Ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, Phenoline ring, phenanthroline ring, indole ring, quinone ring , benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc., and preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, tathazole ring, ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring.

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

Among them, Y ² is preferably a benzene ring or a cyclohexane ring in terms of ease of synthesis.

In the above formula [1], Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, but the alkylene group may be any of a linear, branched or cyclic group, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other. In the above formula [1], Y ⁴ represents a single bond, or represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted by a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

The heterocyclic ring and the alkyl group or the like listed as a substituent may be those listed above for Y ² .

Furthermore, ^Y4 may be a divalent organic group selected from organic groups having 17 to 30 carbon atoms and having a steroid skeleton. Preferred examples thereof are divalent groups having a structure selected from cholesterol, androstenone, β-cholesterol, epiandrostenone, ergosterol, estrone, 11α-hydroxymethylsterol, 11α-progesterone, lanostane, ethinylestradiol methyl ether, methyltestosterone, norethindrone, pregnenolone, β-sitosterol, stigmasterol, testosterone, and cholesterol acetate, etc., with two hydrogen atoms removed. More specifically, the following examples are provided. (Wherein, * represents the bonding position).

Among them, Y ⁴ is preferably a benzene ring, a cyclohexane ring or a divalent organic group having 17 to 30 carbon atoms and having a steroid skeleton in terms of ease of synthesis.

In formula [1], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted with a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. The heterocyclic ring and the alkyl group listed as a substituent may be those listed in the above Y ⁴ .

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

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

In formula [1], Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorinated alkoxy group having 1 to 18 carbon atoms. The alkyl group having 1 to 18 carbon atoms, the fluorinated alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, and the fluorinated alkoxy group having 1 to 18 carbon atoms may be in a linear, branched, or cyclic form, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other.

Among them, ^Y6 is preferably an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorinated alkoxy group having 1 to 10 carbon atoms. ^Y6 is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. It is particularly preferred that ^Y6 is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

Furthermore, when ^Y4 is a divalent organic group having a steroid skeleton, ^Y6 is preferably a hydrogen atom.

For example, the alkyl group having 1 to 18 carbon atoms includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1 -butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1,1-dimethyl-n-pentyl, 1,2-dimethyl-n-pentyl, 1,3-dimethyl-n-pentyl, 2 ,2-dimethyl-n-pentyl, 2,3-dimethyl-n-pentyl, 3,3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1,1-dimethyl-n-hexyl, 1,2-dimethyl-n-hexyl, 1,3-dimethyl -n-hexyl, 2,2-dimethyl-n-hexyl, 2,3-dimethyl-n-hexyl, 3,3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, etc.

As the above-mentioned alkylene group having 1 to 15 carbon atoms, a divalent group formed by removing one arbitrary hydrogen atom from the above-mentioned alkyl group can be cited. 　　As the above-mentioned alkoxy group having 1 to 18 carbon atoms, a group formed by bonding an oxygen atom -O- to the group cited as a specific example of the above-mentioned alkyl group can be cited. 　　Furthermore, as the above-mentioned fluorinated alkyl group having 1 to 18 carbon atoms and fluorinated alkoxy group having 1 to 18 carbon atoms, a group formed by replacing an arbitrary hydrogen atom in the above-mentioned alkyl group having 1 to 18 carbon atoms and alkoxy group having 1 to 18 carbon atoms with a fluorine atom can be cited.

Furthermore, when ^Y2 and ^Y3 represent groups other than single bonds, the bond between ^Y2 and ^Y3 may be a single bond or may be through a bonding group A; when ^Y3 and ^Y4 represent groups other than single bonds, the bond between ^Y3 and ^Y4 may be a single bond or may be through a bonding group A; when ^Y4 and ^Y5 represent groups other than single bonds, the bond between ^Y4 and ^Y5 may be a single bond or may be through a bonding group A; when ^Y5 and ^Y6 represent groups other than single bonds, the bond between ^Y5 and ^Y6 may be a single bond or may be through a bonding group A; when n is 2 or more, one ^Y5 and the adjacent Y The bond between ⁵ can be a single bond or can be through a bonding group A.

The above-mentioned bonding group A represents a group selected from the group consisting of -O-, _-CH2O- , -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-CO-O-, -O-CO-NH- and -NH-CO-NH-.

The total number of carbon atoms contained in the group represented by formula [1] is 6 to 30, for example 6 to 20.

Among them, when considering the vertical alignment property and the coating property of the polymerizable liquid crystal, the vertical alignment group represented by formula [1] is preferably a group containing 7 to 18 carbon atoms, especially an alkyl group containing 8 to 15 carbon atoms, and is more preferably an alkyl group containing 7 to 18 carbon atoms, especially 8 to 15 carbon atoms.

The method for obtaining the polymer of the component (A) of the present invention is not particularly limited. For example, the polymer of the component (A) can be obtained by reacting a monomer having a vertically aligning group with an arbitrary monomer by a polymerization method such as free radical polymerization.

Specific examples of arbitrary monomers are given below, but are not limited to them.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl)phthalate, mono-(2-(methacryloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

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

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, 2-(acryloyloxy)ethyl caprolactone, 2-(methacryloyloxy)ethyl caprolactone, poly(ethylene glycol)ethyl ether acrylate, poly(ethylene glycol)ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone.

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

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

Examples of the monomer having an isocyanate group include acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, and m-tetramethylxylene isocyanate.

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenyl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracenylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclopentyl methacrylate, methacrylate, 2-hexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

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

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

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

The weight average molecular weight of the polymer of component (A) is preferably 1,000 to 200,000, more preferably 2,000 to 150,000, and even more preferably 3,000 to 100,000. If the weight average molecular weight is too large, exceeding 200,000, the solubility in the solvent is reduced and the workability is reduced. If the weight average molecular weight is too small, less than 1,000, the solvent resistance and heat resistance are reduced.

In the polymer of component (A), the proportion of the vertical alignment group per 100 mol of the total repeating units of the polymer is preferably 3 mol% to 90 mol%, and more preferably 5 mol% to 80 mol%. If it is less than 3 mol%, the vertical alignment will be insufficient, and if it is greater than 90 mol%, there is a possibility of adversely affecting the coating properties of the liquid crystal.

As the polymer having a vertical alignment group, commercially available products can be suitably used, for example, ARUFON UF-5041, UF-5080, UF-5022 [all manufactured by Toa Gosei Co., Ltd.] and the like can be cited.

＜Component (B)＞ 　　In the curing film forming composition of the present invention, component (B) is a compound having two or more polymerizable groups containing a C=C double bond. 　　As the polymerizable group containing a C=C double bond, there can be cited an acrylic group, a methacrylic group, a vinyl group, an allyl group, a maleimide group, and the like.

The polymerizable group containing a C=C double bond of the component (B) preferably has 3 to 16 carbon atoms and an unsaturated bond at the terminal, and a specific side chain represented by formula (b2) is particularly preferred.

In formula (b2), R ⁵¹ is an organic group having 1 to 14 carbon atoms and selected from the group consisting of aliphatic groups, aliphatic groups including cyclic structures, and aromatic groups, or a combination of a plurality of organic groups selected from the group. R ⁵¹ may include an ester bond, an ether bond, an amide bond, or a urethane bond. In formula (b2), R ⁵² is a hydrogen atom or a methyl group, and a specific side chain in which R ⁵² is a hydrogen atom is preferred, and a specific side chain having an acryl group, a methacryl group, or a styryl group at the end is more preferred.

In addition, the (meth)acrylic compound in this specification refers to both acrylic compounds and methacrylic compounds. For example, (meth)acrylic acid is referred to as acrylic acid and methacrylic acid. In addition, (meth)acryloyl represents CH ₂ =CHCO- and CH(CH ₃ )=CHCO-.

The following are examples of suitable compounds as the compound having a polymerizable group including a C=C double bond, but the component (B) is not limited to these examples.

Examples of the compound having two (meth)acryloyl groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol ... di(meth)acrylate, tricyclo[5.2.1.02,6]decanedimethanol di(meth)acrylate, dioxanediol di(meth)acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di(meth)acryloyloxypropane, trishydroxyethyl isocyanurate di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, undecenyloxyethylene glycol di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and the like.

As the compound having two or more (meth)acryloyl groups, commercially available products can be suitably used, for example, Lightacrylate 3EG-A, Lightacrylate 4EG-A, Lightacrylate 9EG-A, Lightacrylate 14EG-A, Lightacrylate PTMGA-250, Lightacrylate NP-A, Lightacrylate MPD-A, Lightacrylate 1.6HX-A, Lightacrylate 1.9ND-A, Lightacrylate MOD-A, Lightacrylate DCP-A, Lightacrylate BP-4EAL, Lightacrylate BP-4PA, Lightacrylate HPP-A, Lightester G-201P, Lightester P-2M, Lightester EG, Lightester 2EG, Lightester 3EG, Lightester 4EG, Lightester 9EG, Lightester 14EG, Lightester 1.4BG, Lightester NP, Lightester 1.6HX, Lightester 1.9ND, Lightester G-101P, Lightester G-201P, Lightester BP-2EMK [All of the above are made by Kyoei Chemical Co., Ltd.]; NK Ester701A, same as A-200, same as A-400, same as A-600, same as A-1000, same as A-B1206PE, same as ABE-300, same as A-BPE-10, same as A-BPE-20, same as A-BPE-30, same as A-BPE-4, same as A-BPEF, same as A-BPP-3, same as A-DCP, same as A-DOD-N, same as A-HD-N, same as A-NOD-N, same as APG-100, same as APG-200, same as APG-400, same APG-700, same as A-PTMG-65, same as 1G, same as 2G, same as 3G, same as 4G, same as 9G, same as 14G, same as 23G, same as BPE-80N, same as BPE-100, same as BPE-200, same as BPE-500, same as BPE-900, same as BPE-1300N, same as DCP, same as DCP-N, same as HD-N, same as NOD-N, same as NPG, same as 1206PE, same as 701, same as 9PG [all of the above are made by Shin-Nakamura Chemical Industry Co., Ltd.]; FANCRYL FA-124AS, same as FA-129AS, same as FA-222A, same as FA-240A, same as FA-P240A, same as FA-P270A, same as FA-321A, same as FA-324A, same as FA-PTG9A, same as FA-121M, same as FA-124M, same as FA-125M, same as FA-220M, same as FA-240M, same as FA-320M, same as FA-321M, same as FA-3218M, same as FA-PTG9M [all manufactured by Hitachi Chemical Co., Ltd.]; D PGDA, HODA, TPGDA, EBECRYL (registered trademark) 145, same as 150, IRR214-K, PEG400DA-D, EBECRYL (registered trademark) 11, HPDNA [manufactured by Daicel-allnex (Co., Ltd.)]; Viscoat #195, same as #230, same as #260, same as #310HP, same as #335HP, same as #700HV, same as #540, same as #802, same as #295 [all manufactured by Nippon Synthetic Chemical Industry (Co., Ltd.)], etc.

Examples of the compound having three (meth)acryloyl groups (trifunctional compound) include ethylene oxide-modified 1,1,1-trihydroxymethylethane tri(meth)acrylate [ethylene oxide added molar number 3 to 30], ethylene oxide-modified trihydroxymethylpropane tri(meth)acrylate [ethylene oxide added molar number 3 to 30], propylene oxide-modified trihydroxymethylpropane tri(meth)acrylate [propylene oxide added molar number 3 to 30], ethylene oxide-modified glycerol tri(meth)acrylate [ethylene oxide added molar number 3 to 30], and ethylene oxide-modified 1,1,1-trihydroxymethylethane tri(meth)acrylate. ], propylene oxide modified glycerol tri(meth)acrylate [propylene oxide addition molar number 3~30], tris(2-(acryloyloxy)ethyl)isocyanurate, ε-caprolactone modified tris(2-(acryloyloxy)ethyl)isocyanurate [ε-caprolactone addition molar number 1~30], 1,1,1-trihydroxymethylethane tri(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ditrihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, etc.

The trifunctional compound can be commercially available, for example, Viscoat#360 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; NK Ester A-GLY-9E, A-GLY-20E, AT-20E [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [all manufactured by Daicel-allnex Co., Ltd.], Viscoat#295, PE-300 [all manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Lightacrylate TMP-A, PE-3A, Lightester TMP [all manufactured by Kyoeisha Chemical Co., Ltd.]; NK EsterA-9300, same as A-9300-1CL, same as A-TMM-3, same as A-TMM-3L, same as A-TMM-3LM-N, same as A-TMPT, same as TMPT [all of the above are made by Shin-Nakamura Chemical Industry (Co., Ltd.)]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [all of the above are made by Daicel-allnex (Co., Ltd.)], etc.

Examples of the compound having four (meth)acryloyl groups (tetrafunctional compound) include ethylene oxide-modified ditrihydroxymethylpropane tetra(meth)acrylate [ethylene oxide addition molar number 4 to 40], ethylene oxide-modified pentaerythritol tetra(meth)acrylate [ethylene oxide addition molar number 4 to 40], ditrihydroxymethylpropane tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

The above-mentioned four-functional compound is a commercially available product, for example, NK Ester ATM-4E, ATM-35E [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 40 [manufactured by Daicel-Allnex Co., Ltd.], Viscoat #300 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Lightacrylate PE-4A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester AD-TMP, A-TMMT [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 140, 1142, 180 [all manufactured by Daicel-Allnex Co., Ltd.], etc.

Examples of the compound having five or more (meth)acryloyl groups (pentafunctional or higher compounds) include ethylene oxide-modified dipentaerythritol hexa(meth)acrylate [ethylene oxide addition molar number 6 to 60], ethylene oxide-modified tripentaerythritol octa(meth)acrylate [ethylene oxide addition molar number 6 to 60], dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, and the like.

The above-mentioned pentafunctional or higher compounds are commercially available products, for example, NK Ester A-DPH-12E [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.], Viscoat #802 [manufactured by Osaka Organic Chemical Industry Co., Ltd.]; Lightacrylate DPE-6A [manufactured by Kyoeisha Chemical Co., Ltd.]; NK Ester A-9550, Tong A-DPH [all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; DPHA [manufactured by Daicel-allnex Co., Ltd.], etc.

Examples of the bifunctional urethane (meth)acrylate include a urethane compound of a (meth)acrylic acid adduct of phenyl glycidyl ether and hexamethylene diisocyanate, and a urethane compound of a (meth)acrylic acid adduct of phenyl glycidyl ether and toluene diisocyanate.

The above-mentioned bifunctional urethane (meth) acrylate is a commercially available product, for example, AH-600, AT-600 [all of which are manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-2PPA, U-200PA, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-W2A [all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 210, 215, 230, 244, 245, 270, 280/15IB, 284, 285, 4858, 8307, 8402, 8411, 8804, 88 07. Same as 9227EA, 9270, KRM (registered trademark) 7735 [all manufactured by Daicel-allnex (Co., Ltd.)]; Unisplendour (registered trademark) UV-6630B, 7000B, 7461TE, 2000B, 2750B, 3000, 3200B, 3210EA, 3300B, 3310B, 3500BA, 3520TL, 3700B, 6640B [all manufactured by Nippon Gosei Kagaku Kogyo (Co., Ltd.)], etc.

Specific examples of commercially available products of the polyfunctional urethane (meth)acrylate compound having three (meth)acryl groups include NK Oligo UA-7100 [manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 204, 205, 264, 265, 294/25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, 8667 [all manufactured by Daicel-Allnex Co., Ltd.]; and UV-7550B, 7000B, 7510B, 7461TE, 2750B [all manufactured by Nippon Gosei Chemical Industry Co., Ltd.], etc.

Specific examples of commercially available products of the polyfunctional urethane (meth)acrylic compound having four (meth)acryl groups include EBECRYL (registered trademark) 8210, 8405, KRM (registered trademark) 8528 [all manufactured by Daicel-Allnex Co., Ltd.]; and UV-7650B (registered trademark) [manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.].

Examples of the polyfunctional urethane (meth)acrylate compound having five or more (meth)acryl groups (urethane (meth)acrylate having five or more functional groups) include a urethane compound of pentaerythritol tri(meth)acrylate and hexamethylene diisocyanate, a urethane compound of pentaerythritol tri(meth)acrylate and toluene diisocyanate, a urethane compound of pentaerythritol tri(meth)acrylate and isophorone diisocyanate, and a urethane compound of dipentaerythritol penta(meth)acrylate and hexamethylene diisocyanate.

The above-mentioned pentafunctional or higher urethane (meth)acrylates are commercially available products, for example, UA-306H, UA-306T, UA-306I, UA-510H [all manufactured by Kyoeisha Chemical Co., Ltd.]; NK Oligo U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, UA-33H [all manufactured by Shin-Nakamura Chemical Co., Ltd.]; EBECRYL (registered trademark) 220, 1290, 5129, 8254, 8301R, KRM (registered trademark) 8200, 82 00AE, 8904, 8452 [all manufactured by Daicel-allnex (Co., Ltd.)]; Tsinghua (registered trademark) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, 7650B [all manufactured by Nippon Synthetic Chemical Industry (Co., Ltd.)], etc.

The component (B) of the present invention may be a polymer compound having one or more side chains with polymerizable unsaturated bonds at the ends in the molecule. As such a polymer compound having side chains with polymerizable unsaturated bonds at the ends, a polymer compound having (meth)acryloyl groups on two or more side chains in the molecule is preferably exemplified.

Examples of the polymer compound include polymer compounds containing one or more (meth)acryl groups, such as urethane acrylate-based polymers, epoxy acrylate-based polymers, and various (meth)acrylate-based polymers.

The weight average molecular weight of the polymer compound of component (B) is preferably 1,000 to 200,000, more preferably 5,000 to 50,000. If the molecular weight is less than 1,000, the effect of the present invention cannot be exerted. On the other hand, if the molecular weight is too large, exceeding 100,000, there is a possibility that the polymer compound will not dissolve in the composition.

Examples of such compounds of the component (B) include polymers such as ACRIT 8BR-930M, 8UH-1006, 8KQ-2001, 8KX-078, 1SX-1055 [all manufactured by Taisei Fine Chemical Co., Ltd.], SMP-250A, SMP-360A, SMP-550A [all manufactured by Kyoeisha Chemical Co., Ltd.], and the like.

When the component (B) is contained, the content is 10 to 2000 parts by mass, preferably 15 to 500 parts by mass, per 100 parts by mass of the component (A).

＜Component (C)＞ 　　Component (C) in the curing film forming composition of the present invention is a free radical polymerization initiator. 　　As the free radical polymerization initiator, well-known ones can be used, for example, alkyl phenones, benzophenones, acyl phosphine oxides, Michell's benzoyl benzoate, oxime esters, tetramethylthiuram monosulfide, thioxanthones, etc. can be cited.

As the free radical polymerization initiator used in the present invention, there can be mentioned, for example, α-diketones such as diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.; benzophenones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone; acetophenone, p-dimethylaminoacetophenone, α,α-dimethoxy-α-acetyloxyacetophenone, α,α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 1-[2-methyl-4-methylphenylthio]-2-morpholinyl-1-propanethone; Acetophenones such as anthraquinone, α,α-dimethoxy-α-morpholinyl-methylphenylthioacetophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, etc.; quinones such as anthraquinone and 1,4-naphthoquinone, etc.; halogen compounds such as benzylmethyl chloride, tribromomethylbenzene, and tris(trichloromethyl)-s-triazine, etc.; bisimidazoles such as [1,2'-biimidazole]-3,3',4,4'-tetraphenyl and [1,2'-biimidazole]-1,2'-dichlorophenyl-3,3',4,4'-tetraphenyl, etc.; peroxides such as di-tert-butyl peroxide; acylphosphine oxides such as 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. As commercially available products, there are those sold under the trade names of Irgacure 184, 369, 379EG, 651, 500, 907, CGI369, CG24-61 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin LR8728, Lucirin TPO (all manufactured by BASF Co., Ltd.), Darocur 1116, 1173 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), and Ubecryl P36 (manufactured by UCB Co., Ltd.).

Among the above, 1-[2-methyl-4-methylphenylthio]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, acetophenones such as α,α-dimethoxy-α-phenylacetophenone, benzylmethyl chloride, tribromomethylphenylsulfonium, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 1,2'-bisimidazoles, and a combination of 4,4'-diethylaminobenzophenone and hydrothiobenzothiazole are preferred. Lucirin TPO (trade name), Irgacure 651 (trade name), and Irgacure 369 (trade name) are preferred.

The above-mentioned free radical polymerization initiator can be used alone or in combination of two or more. The above-mentioned free radical polymerization initiator can be used in an amount of preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 30 parts by mass relative to 100 parts by mass of component (A). If the amount of the free radical polymerization initiator used is less than the above-mentioned range, it is easily affected by the passivation of free radicals caused by oxygen (reduction in sensitivity), and if it is more than the above-mentioned range, there will be a tendency for the compatibility to deteriorate or the storage stability to decrease.

<Solvent> The curable film forming composition of the present invention is mainly used in the form of a solution dissolved in a solvent. The solvent used at this time is not particularly limited as long as it can dissolve the (A) component, the (B) component and the (C) component and other additives described later as required.

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 monoethyl ether, methyl solvent, ethyl solvent, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl -2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

When the hardened film forming composition of the present invention is used to form a hardened film on a resin film to manufacture an alignment 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 preferred as solvents to which the resin film exhibits resistance. 　　These solvents can be used alone or in combination of two or more.

<Other additives> Furthermore, the curing film forming composition of the present invention may contain sensitizers, adhesion enhancers, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, preservation stabilizers, defoaming agents, antioxidants, etc. as needed, as long as the effects of the present invention are not impaired.

<Preparation of Curable Film Forming Composition> The curable film forming composition of the present invention is a composition comprising a polymer having a vertically oriented group as component (A), a compound having two or more polymerizable groups containing a C=C double bond as component (B), and a polymerization initiator as component (C), and may further contain other additives as long as the effects of the present invention are not impaired. It is usually used in the form of a solution dissolved in a solvent.

Preferred examples of the cured film forming composition of the present invention are as follows. [1]: A cured film forming composition comprising component (A), component (B) (10 parts by mass to 2000 parts by mass based on 100 parts by mass of component (A), and component (C) (0.1 parts by mass to 50 parts by mass relative to 100 parts by mass of the polymer of component (A)). [2]: A cured film forming composition comprising component (A), component (B) (10 parts by mass to 2000 parts by mass based on 100 parts by mass of component (A), component (C) (0.1 parts by mass to 50 parts by mass relative to 100 parts by mass of the polymer of component (A)), and a solvent.

The following describes in detail the mixing ratio, preparation method, etc. when the curable film forming composition of the present invention is used as a solution. The ratio of the solid content in the curable film forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, and is 1 mass% to 60 mass%, preferably 2 mass% to 50 mass%, and more preferably 2 mass% to 20 mass%. Here, the so-called solid content refers to the components after removing the solvent from all the components of the curable film forming composition.

The method for preparing the cured film forming composition of the present invention is not particularly limited. Examples of the preparation method include a method of preparing a uniform solution by mixing component (B) and then component (C) in a predetermined ratio in a solution of component (A) dissolved in a solvent, or a method of adding and mixing other additives as needed at an appropriate stage of the preparation method.

Furthermore, the prepared solution of the cured film forming composition is preferably filtered using a filter having a pore size of about 0.2 μm or the like before use.

＜Curing film, alignment material and phase difference material＞ A solution of the curing film forming composition of the present invention is applied to a substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal (e.g., aluminum, molybdenum, chromium, etc.) coated substrate, a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film substrate (e.g., a triacetyl cellulose (TAC) film, a polycarbonate (PC) film, a cycloolefin polymer (COP) film, a cycloolefin copolymer The coating is applied on a resin film such as a (COC) film, a polyethylene terephthalate (PET) film, an acrylic film, a polyethylene film, etc., by rod coating, spin coating, flow coating, roll coating, slot coating, slot coating followed by spin coating, inkjet coating, printing, etc., to form a coating film, and then, it is heated and dried using a heating plate or an oven, etc., to form a cured film. The cured film can be directly used as an alignment material.

As the conditions for heat drying, as long as the components of the cured film (alignment material) are not dissolved in the polymerizable liquid crystal solution applied thereon and can be crosslinked by the crosslinking agent, the heating temperature and heating time can be appropriately selected from the range of 60°C to 200°C and 0.4 minutes to 60 minutes. The heating temperature and heating time are preferably 70°C to 160°C and 0.5 minutes to 10 minutes.

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

The alignment material formed by the cured film composition of the present invention has solvent resistance and heat resistance, so a phase difference material such as a polymerizable liquid crystal solution having a vertical alignment property can be coated on the alignment material and aligned on the alignment material. In addition, by directly curing the phase difference material in an aligned state, the phase difference material can be formed as a layer having optical anisotropy. In addition, if the substrate on which the alignment material is formed is a thin film, it is useful as a phase difference film.

Furthermore, by using two substrates having the alignment material of the present invention formed in the above-mentioned manner, laminating them with the alignment materials on the two substrates facing each other via a spacer, and then injecting liquid crystal between the substrates, a liquid crystal display element with the liquid crystal already aligned can also be produced. 　　The cured film-forming composition of the present invention can be suitable for use in the manufacture of various phase difference materials (phase difference films) or liquid crystal display elements, etc. [Example]

The following is a detailed description of the present invention by giving examples, but the present invention is not limited to these examples. [Codes used in the examples] The meanings of the codes used in the following examples are as follows. < (A) Raw materials of components > LAA: lauryl acrylate MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate MA1: AIBN: α,α'-azobisisobutyronitrile ARU: ARUFON UF-5041 manufactured by Toagosei Co., Ltd. <(B) Component> DPHA: Dipentaerythritol hexaacrylate 8KX: 8KX-078 manufactured by Taisei Fine Chemical Co., Ltd. (solid concentration: 40 mass%) 8KQ: 8KQ-2001 manufactured by Taisei Fine Chemical Co., Ltd. (solid concentration: 39 mass%) 8UH: 8UH-1006 manufactured by Taisei Fine Chemical Co., Ltd. (solid concentration: 45 mass%) <(C) Component> IRG: IRGACURE 907 manufactured by BASF <Solvent> Each resin composition of the Examples and Comparative Examples contains a solvent, and propylene glycol monomethyl ether (PM), ethyl acetate (EA) and butyl acetate (BA) are used as the solvent. <Determination of molecular weight of polymer> The molecular weight of the acrylic acid copolymer in the polymerization example was measured using a GPC device manufactured by Shimadzu Corporation (Shodex (registered trademark) columns KF803L and KF804L) in the following manner. In addition, the number average molecular weight (hereinafter referred to as Mn) and number average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene conversion. Solvent: Tetrahydrofuran Flow rate: 1 mL/min Column temperature: 40°C Calibration line standard sample: Showa Denko polystyrene (molecular weight of approximately 197,000, 55,100, 12,800, 3,950, 1,260, 580)

＜Synthesis Example 1＞ Synthesis of MA1 4.0 g (14.6 mmol) of 4-(trans-4-pentylcyclohexyl)benzoic acid, 1.0 g (13.3 mmol) of HEMA, 2.5 g (15.9 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 0.1 g (0.7 mmol) of 4-dimethylaminopyridine, and 19.3 g of tetrahydrofuran were mixed and stirred at room temperature for 24 hours. After the reaction was completed, tetrahydrofuran was distilled off under reduced pressure, dissolved in 150 mL of ethyl acetate, and 100 mL of ammonium chloride aqueous solution was added and washed three times. The ethyl acetate was distilled off under reduced pressure to obtain 4.3 g of the target MA1 (yield: 84%). ＜Polymerization Example 1＞ 1.0 g of LAA, 3.2 g of MAA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 15.3 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content: 20% by mass) (P1). The obtained acrylic copolymer had an Mn of 5,500 and an Mw of 7,100.

＜Polymerization Example 2＞ 1.0 g of LAA, 0.8 g of MAA, and 0.1 g of AIBN as a polymerization catalyst were dissolved in 7.8 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 25% by mass) (P2). The obtained acrylic copolymer had an Mn of 13,700 and an Mw of 24,000.

＜Polymerization Example 3＞ 1.0 g of LAA, 3.7 g of MMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 15.3 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid content: 25% by mass) (P3). The obtained acrylic copolymer had an Mn of 7,700 and an Mw of 13,600.

＜Polymerization Example 4＞ 　　MMA 3.0g, HEMA 0.3g, and AIBN 0.3g as a polymerization catalyst were dissolved in PM 14.6g, and the mixture was reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 30% by mass) (P4). The Mn of the obtained acrylic copolymer was 18,000, and the Mw was 32,800. ＜Polymerization Example 5＞ 　　MA1 1.0g, MAA 0.8g, and AIBN 0.1g as a polymerization catalyst were dissolved in PM 7.7g, and the mixture was reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (P5). The Mn of the obtained acrylic copolymer was 8,900, and the Mw was 30,800.

<Examples 1 to 11, Comparative Examples 1 to 2> Using the compositions shown in Table 1, each cured film forming composition was prepared.

<Examples 12 to 28, Comparative Examples 3 to 5> Next, each phase difference material morphology composition is used to form a cured film, and the vertical alignment of the obtained cured films is evaluated. [Evaluation of vertical alignment] Using a rod coater, each cured film forming composition obtained in Examples 1 to 11 and Comparative Examples 1 to 2 is coated on each substrate in a wet film thickness of 4 μm. After heating and drying in a heat circulation oven at a temperature of 110°C for 60 seconds, the coated film is exposed to form a cured film on each substrate. Using a rod coater, a polymerizable liquid crystal solution RMS03-015 for vertical alignment manufactured by Merck Co., Ltd. is coated on the cured film in a wet film thickness of 6 μm. After heating and drying on a heating plate at 60°C for 60 seconds, the coating was exposed to 500mJ/ ^cm2 to produce a phase difference material. The prepared phase difference materials were used to measure the incident angle dependence of the in-plane phase difference using the phase difference measurement device RETS100 manufactured by Otsuka Electronics Co., Ltd. The in-plane phase difference value at an incident angle of 0 degrees was 0, and the in-plane phase difference value at an incident angle of ±50 degrees was 38±5nm, which was judged as a vertical alignment. The evaluation results are summarized and shown in the following Table 2.

As shown in Table 2, the alignment material obtained by using the cured film forming composition of the embodiment exhibits good vertical alignment. In contrast, the cured film obtained by using the cured film forming composition of the comparative example is difficult to obtain vertical alignment. [Industrial Applicability]

The cured film-forming composition obtained by the present invention is very useful as a material for forming a liquid crystal alignment film for a liquid crystal display element or an alignment material for an optically anisotropic film provided inside or outside a liquid crystal display element, and is particularly suitable as a material for optical compensation films for circularly polarizing plates used as antireflection films for IPS-LCDs or organic EL displays.

Claims (4)

A cured film forming composition comprising the following components: (A) a polymer having a group represented by the following formula [1] as a vertical alignment group, (B) a compound having two or more polymerizable groups containing a C=C double bond, and (C) a radical polymerization initiator, wherein only the component (B) has a polymerizable group containing a C=C double bond, the component (B) is contained in an amount of 10 parts by mass to 2000 parts by mass based on 100 parts by mass of the component (A), and the component (C) is contained in an amount of 0.1 parts by mass to 50 parts by mass per 100 parts by mass of the component (A).

(In formula [1], ^Y1 represents a single bond, or a bonding group selected from the group consisting of -O-, _-CH2O- , -COO-, -OCO-, -NHCO-, -NH-CO-O-, and -NH-CO-NH-; ^Y2 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or _-CH2 -CH(OH) _-CH2- , or a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, wherein the alkylene group may be 1 to 3 The divalent cyclic group is a cyclic group in which any hydrogen atom may be substituted by a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy 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, wherein the alkylene group may be any one of a linear, branched or cyclic group, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other; Y ^Y represents a single bond, or a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 17 to 30 carbon atoms and a steroid skeleton, wherein any hydrogen atom on the divalent cyclic group may be substituted by a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom; ^Y5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, wherein any hydrogen atom on the divalent cyclic group may be substituted by a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 3 carbon atoms, a linear or branched fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom; n represents an integer of 0 to 4, and when n is 2 or more, the respective ^Y5 may be the same or different; Y ⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorinated alkoxy group having 1 to 18 carbon atoms, wherein the alkyl group having 1 to 18 carbon atoms, the fluorinated alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, and the fluorinated alkoxy group having 1 to 18 carbon atoms may be in a linear, branched, or cyclic form, or a combination thereof, and may be interrupted by 1 to 3 bonding groups A, but the bonding groups A are not bonded to each other; if ^Y2 and ^Y3 represent a group other than a single bond, the bond between ^Y2 and ^Y3 may be a single bond or may be separated by a bonding group A; if ^Y3 and ^Y4 represent a group other than a single bond, ^Y3 and Y4 may be in a linear, branched, or cyclic form, or a combination thereof. The bond between ^Y4 and ^{Y5 may be a single bond or may be through a bonding group A. When Y4 and Y5 represent} groups other than single bonds, the bond between ^Y4 and ^Y5 may be a single bond or may be through a bonding group A. When ^Y5 and ^Y6 represent groups other than single bonds, the bond between ^Y5 and ^Y6 may be a single bond or may be through a bonding group A. When n is 2 or more, the bond between one ^Y5 and the adjacent ^Y5 may be a single bond or may be through a bonding group A. The bonding group A represents -O-, _-CH2 O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH-, but the total number of carbon atoms contained in the group represented by formula [1] is 6 to 30). The cured film forming composition of claim 1, wherein the polymerizable group containing a C=C double bond of component (B) is at least one selected from an acrylic group, a methacrylic group, a vinyl group, an allyl group, and a maleimide group. An alignment material characterized by being obtained by hardening a hardened film forming composition as in claim 1 or 2. A phase difference material characterized by being formed using a cured film obtained from a cured film forming composition as in claim 1 or 2.