KR20200037278A - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

[Problem] A cured film forming composition for providing an alignment material exhibiting good liquid crystal orientation and excellent adhesion to a liquid crystal layer is provided.
[Solutions] (A) A reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a cured film forming composition containing a crosslinking agent, and a cured film, alignment material obtained therefrom, And phase difference.

Description

Cured film forming composition, alignment material and retardation material

The present invention relates to a cured film forming composition for aligning liquid crystal molecules, an alignment material, and a retardation material. Particularly, the present invention is a cured film forming composition, alignment material, and retardation material useful for producing a patterned retardation material used in a circularly polarized glasses type 3D display or a retardation material used in a circular polarizing plate used as an anti-reflection film for an organic EL display. It is about.

In the case of a 3D display of the circularly polarized spectacles method, it is common that a phase difference material is disposed on a display element forming an image such as a liquid crystal panel. In this phase difference material, two or more types of phase difference regions having different phase difference characteristics are arranged regularly and constitute a patterned phase difference material. Meanwhile, in the present specification, a retardation material patterned to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

The patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal, as disclosed in Patent Document 1. The optical patterning of the retardation material made of a polymerizable liquid crystal uses a photo-alignment technique known in the formation of an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two kinds of polarizations having different polarization directions are irradiated thereon. Then, a photo-alignment film is obtained as an alignment material in which two kinds of liquid crystal alignment regions having different alignment control directions of liquid crystals are formed. A phase difference material in a solution phase containing a polymerizable liquid crystal is coated on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Then, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

The anti-reflection film of the organic EL display is composed of a linear polarizing plate and a quarter-wave retardation plate, and converts foreign light toward the panel surface of the image display panel into linear polarization by a linear polarizing plate, followed by a quarter-wave retardation plate. It converts into circularly polarized light. Here, the foreign light by the circularly polarized light is reflected from the surface of the image display panel, etc., and the direction of rotation of the polarizing surface is reversed during this reflection. As a result, the reflected light is converted into linearly polarized light in a direction shielded by the linearly polarized plate by a quarter-wave retardation plate, as opposed to when it arrives, and then shielded by the subsequent linearly polarized plate. The emission of is significantly suppressed.

With respect to this quarter-wave retardation plate, in Patent Document 2, a quarter-wave retardation plate is formed by combining a half-wave plate and a quarter-wave plate, thereby constituting the optical film according to the reverse dispersion characteristics. A method has been proposed. In the case of this method, in the wide wavelength band provided for the display of a color image, an optical film may be constructed according to the reverse dispersion characteristic by using a liquid crystal material according to the positive dispersion characteristic.

In addition, recently, as a liquid crystal material applicable to the retardation layer, it has been proposed to have inverse dispersion characteristics (Patent Documents 3 and 4). According to the liquid crystal material having such a reverse dispersion characteristic, instead of forming a quarter-wave retardation plate by a two-layer retardation layer by combining a half-wave plate and a quarter-wave plate, a retardation layer is composed of a single layer. By doing so, it is possible to secure the inverse dispersion characteristic, and accordingly, an optical film capable of securing a desired phase difference in a wide wavelength band can be realized by a simple configuration.

An alignment layer is used to align the liquid crystal. As a method for forming an alignment layer, for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method is useful in that it does not generate static electricity or dust, which is a problem of the rubbing method, and can control quantitative alignment processing. .

In the formation of the alignment material using the photo-alignment method, as an available photo-alignment material, there are known acrylic resins, polyimide resins, etc. having light dimerization sites such as cinnamoyl groups and chalcone groups on the side chains. It has been reported that these resins exhibit the ability to control the alignment of liquid crystals (hereinafter, also referred to as liquid crystal alignment properties) by irradiating polarized UV (see Patent Documents 5 to 7).

Further, in addition to the liquid crystal alignment ability, the alignment layer is required to have adhesiveness with the liquid crystal layer. For example, when the adhesion between the alignment layer and the liquid crystal layer formed thereon is insufficient, the liquid crystal layer may peel off in a winding step included in the production of the retardation film.

Japanese Patent Publication No. 2005-49865 Japanese Patent Publication H10-68816 US Patent No. 8119026 Japanese Patent Publication 2009-179563 Japanese Patent No. 3611342 Japanese Patent Publication 2009-058584 Japanese Patent Publication No. 2001-517719

The object of the present invention was achieved based on the above findings and examination results. That is, an object of the present invention is to provide a cured film forming composition for providing an alignment material exhibiting good liquid crystal orientation and excellent adhesion to a liquid crystal layer.

Other objects and advantages of the present invention will become apparent from the following description.

In order to achieve the above object, the present inventors, after repeated polite reviews, (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, (B) curing based on a crosslinking agent By selecting the film-forming composition, it was found that a cured film exhibiting good liquid crystal orientation and excellent adhesion to the liquid crystal layer can be formed, thereby completing the present invention.

That is, as the first aspect, the present invention relates to a cured film forming composition containing (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a crosslinking agent.

As a 2nd viewpoint, the group containing the said polymerizable double bond is related with the cured film formation composition as described in 1st viewpoint which is a (meth) acryloyl group.

As a third aspect, the cinnamic acid derivative having a group containing a polymerizable double bond relates to the cured film forming composition according to the first aspect or the second aspect, which is a compound represented by the following formula (1).

[Formula 1]

In Formula (1), A ¹ and A ² each independently represent a hydrogen atom or a methyl group,

R ¹ is the following formula (c-2)

[Formula 2]

(In formula (c-2), the broken line represents a bonding hand, R ¹⁰¹ represents an alkylene group having 1 to 30 carbon atoms, and one or a plurality of hydrogen atoms in the alkylene group is a fluorine atom or an organic group. In addition, -CH ₂ CH ₂ -in R ¹⁰¹ may be substituted with -CH = CH-, and further, -O- in the case where any of the following groups are not adjacent to each other. , -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO- may be substituted with a group selected from the group consisting of, M ¹ represents a hydrogen atom or a methyl group .) Represents a group,

R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group,

R ³ represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-,

R ⁴ to R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, And a substituent selected from the group consisting of nitro groups,

Further, R ² , R ³ and R ⁴ or R ² , R ³ and R ⁶ may be united to form an aromatic group,

n is an integer from 0 to 3.)

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

As a fifth aspect, any one of the first to fourth aspects further comprising a polymer having at least one group selected from the group consisting of (C) a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. It relates to the cured film forming composition described.

As a 6th viewpoint, it is related with the cured film formation composition in any one of 1st viewpoint-5th viewpoint which further contains (D) crosslinking catalyst.

In a seventh aspect, (E) at least one group A selected from the group consisting of at least one polymerizable group, a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or at least one group reacting with the group A It is related with the cured film formation composition in any one of 1st viewpoint-6th viewpoint containing the compound which has group.

As 8th viewpoint, it is related with the cured film formation composition in any one of 1st viewpoint-7th viewpoint containing 1 mass part-500 mass parts (B) component based on 100 mass parts of (A) component.

As a ninth aspect, according to any one of the fifth aspect to the eighth aspect containing 1 part by mass to 400 parts by mass of the component (C) relative to 100 parts by mass, which is the total amount of the crosslinking agent of the component (A) and the component (B). It relates to the cured film forming composition described.

As a tenth aspect, according to any one of the sixth to ninth aspects, containing 0.01 parts by mass to 20 parts by mass of the (D) component relative to 100 parts by mass, which is the total amount of the crosslinking agent of the component (A) and the component (B). It relates to the cured film forming composition described.

As an eleventh aspect, according to any one of the seventh to tenth aspects containing 1 part by mass to 100 parts by mass of the (E) component relative to 100 parts by mass, which is the total amount of the crosslinking agent of the component (A) and the component (B). It relates to the cured film forming composition described.

As a 12th viewpoint, it is related with the cured film characterized by being obtained from the cured film formation composition in any one of 1st viewpoint-11th viewpoint.

As a 13th viewpoint, it is related with the orientation material characterized by being obtained from the cured film formation composition in any one of 1st viewpoint-11th viewpoint.

As a 14th viewpoint, it is related with the phase difference material characterized by being formed using the cured film obtained from the cured film formation composition in any one of 1st viewpoint-11th viewpoint.

ADVANTAGE OF THE INVENTION According to this invention, the cured film which shows favorable liquid crystal orientation property and is excellent in adhesiveness with a liquid crystal layer, and the cured film formation composition suitable for the formation can be provided. According to the present invention, it is possible to provide an alignment material excellent in liquid crystal alignment and light transmittance. Further, according to the present invention, it is possible to provide a phase difference material capable of high-precision optical patterning.

<Cure film forming composition>

The cured film forming composition of the present invention contains a reaction product of (A) a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a crosslinking agent. The composition for forming a cured film of the present invention is selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group in addition to the (A) component and the (B) component. It may also contain a polymer having at least one group. Furthermore, a crosslinking catalyst can also be included as (D) component. Further, as the component (E), at least one group A selected from the group consisting of at least one polymerizable group, a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least one group reacting with the group A It may contain a compound. In addition, other additives may be contained as long as the effects of the present invention are not impaired.

Hereinafter, details of each component will be described.

<(A) component>

The component (A) contained in the cured film forming composition of the present invention is a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond.

<Polymer having an epoxy group>

The polymer having an epoxy group may be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds.

Specific examples of the polymerizable unsaturated compound having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl acrylate-α-ethyl acrylate, glycidyl acrylate, α-n- Glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethylacrylic acid And -6,7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, and the like.

Other polymerizable unsaturated compounds include (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, and maleimide compounds. , Unsaturated aromatic compounds, conjugated diene-based compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and polymerizable unsaturated compounds other than these.

As specific examples of these, as the alkyl methacrylate ester, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate , Diethylene glycol monomethacrylate, 2,3-dihydroxypropylmethacrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenylmethacrylate, methylmethacrylate, ethylmethacrylate, n -Butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, etc .; As an acrylic acid alkyl ester, For example, methyl acrylate, isopropyl acrylate, etc .; As a methacrylic acid cyclic alkyl ester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, tricyclo [5.2. 1.0 ^2,6 ] decan-8- ^yloxyethyl methacrylate, isoboronil methacrylate, cholestanyl methacrylate, and the like; As the acrylic acid cyclic alkyl ester, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate, tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxyethyl acrylate, isobornyl acrylate, cholestanyl acrylate, etc .; As a methacrylic acid aryl ester, phenyl methacrylate, benzyl methacrylate, etc .; As an acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate, etc .; Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconic acid, and the like; Bicyclounsaturated compounds, for example, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept -2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'- Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2 .1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, etc .; As maleimide compounds, for example, phenyl maleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinate Imidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide, etc .; As unsaturated aromatic compounds, for example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc .; As the conjugated diene-based compound, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc .; As an unsaturated monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .; As unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .; As an unsaturated dicarboxylic acid anhydride, each anhydride of the said unsaturated dicarboxylic acid; Examples of the polymerizable unsaturated compound other than the above include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate, respectively.

The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group is preferably 30% by mass or more, and more preferably 50% by mass or more.

Synthesis of the polymer having an epoxy group can be preferably performed by a known radical polymerization method in a solvent in the presence of a suitable polymerization initiator.

A commercial item can also be used as a polymer which has an epoxy group. As such commercial products, for example, EHPE3150, EHPE3150CE (above, Daicel (former Daicel Chemical Industry Co., Ltd.)), UG-4010, UG-4035, UG-4040, UG-4070 (above, Toa Synthetic ALUFON series), ECN-1299 (Asahi Chemical Co., Ltd.), DEN431, DEN438 (above, manufactured by Dow Chemical), jER-152 (Mitsubishi Chemical Co., Ltd. (formerly Japan Epoxy Resin Co., Ltd.) )), Epiclon N-660, N-665, N-670, N-673, N-695, N-740, N-770, N-775 (above, DIC Corporation (formerly Dai Nippon Inki Chemicals) Industrial Co., Ltd.), EOCN-1020, EOCN-102S, EOCN-104S (above, manufactured by Nippon Chemical Co., Ltd.) and the like.

<Cinnamic acid derivative having a group containing a polymerizable double bond>

As the polymerizable double bond, a double bond between carbon and carbon is preferable. Examples of the group containing the carbon-carbon double bond include a vinyl group, a (meth) acryloyl group, and an acrylamide group, and a (meth) acryloyl group is preferable.

As the cinnamic acid derivative having a group containing a polymerizable double bond, a compound represented by the following formula (1) is preferable.

[Formula 3]

In Formula (1), A ¹ and A ² each independently represent a hydrogen atom or a methyl group,

R ¹ is the following formula (c-2)

[Formula 4]

(In the formula (c-2), the broken line represents a bond, R ¹⁰¹ represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms in the alkylene group may be substituted with a fluorine atom or an organic group. Further, -CH ₂ CH ₂ -in R ¹⁰¹ may be substituted with -CH = CH-, and further, when any one of the following groups is not adjacent to each other, -O-, -NHCO It may be substituted with a group selected from the group consisting of-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, and M ¹ represents a hydrogen atom or a methyl group.) Represents the displayed group,

R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group,

R ³ represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-,

R ⁴ to R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, And a substituent selected from the group consisting of nitro groups,

Further, R ² , R ³ and R ⁴ or R ² , R ³ and R ⁶ may be united to form an aromatic group,

n is an integer from 0 to 3.)

As the divalent aromatic group of R ² , for example, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6 -Tetrafluoro-1,4-phenylene group and the like; Examples of the divalent alicyclic group of R ² include 1,2-cyclopropylene group, 1,3-cyclobutylene group, and 1,4-cyclohexylene group; Examples of the divalent heterocyclic group of R ² include 1,4-pyridylene group, 2,5-pyridylene group, and 1,4-furanylene group; Examples of the divalent condensed cyclic group of R ² include a 2,6-naphthylene group and the like, respectively. R ² is preferably a 1,4-phenylene group.

As a preferable example of the compound represented by said formula (1), the following formulas M1-1-M1-5 are mentioned, for example.

[Formula 5]

(In the formula, M ¹ is a hydrogen atom or a methyl group, s1 represents the number of methylene groups, and is a natural number from 2 to 9.)

The compound represented by the formula (1) can be synthesized by appropriately combining organic chemical methods.

<Reaction of a polymer having an epoxy group and a specific cinnamic acid derivative>

The reaction product of the polymer having an epoxy group and a specific cinnamic acid derivative contained in the liquid crystal aligning agent of the present invention is preferably a polymer having an epoxy group as described above and a specific cinnamic acid derivative, preferably in the presence of a catalyst, It can be synthesized by reacting in a suitable organic solvent.

The proportion of cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 1.3 mol, and even more preferably 0.1 to 1 mol of the epoxy group contained in the polymer having an epoxy group. 1.1 mole.

As the organic catalyst that can be used here, a known compound can be used as a so-called curing accelerator that accelerates the reaction between an organic base or an epoxy compound and an acid anhydride.

Examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene; And quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; Preference is given to quaternary organic amines such as tetramethylammonium hydroxide.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylyi Midazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl)- 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2- Cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimelli Tate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s -tree Gin, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanurate adduct of 2-methylimidazole, Isocyanurate adduct of 2-phenylimidazole, isocyanurate adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine Imidazole compounds; Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenylphosphite; Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphospho Onium iodide, ethyl triphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetra Quaternary phosphonium salts such as fluoroborate, tetra-n-butylphosphoniumtetraphenylborate, tetraphenylphosphoniumtetraphenylborate; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 or organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complexes; Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride; Boron compounds such as boron trifluoride and triphenyl borate; Metal halogen compounds such as zinc chloride and stannous chloride; High melting point dispersion type latent curing accelerators, such as amine addition accelerators such as dicyandiamide and adducts of amines and epoxy resins; A microcapsule type latent curing accelerator coating a surface of a curing accelerator such as the imidazole compound, an organophosphorus compound or a quaternary phosphonium salt with a polymer; Amine salt type latent curing agent accelerator; And latent curing accelerators such as a high temperature dissociation type thermal cation polymerization type latent curing accelerator such as Lewis acid salt and Bronsted acid salt.

Among them, preferably, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

The use ratio of the catalyst is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and even more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer having an epoxy group.

Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Of these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products. The solvent is used in an amount such that the solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1% by mass or more, and more preferably 5 to 50% by mass.

The reaction temperature is preferably 0 to 200 ° C, and more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, and more preferably 0.5 to 20 hours.

In this way, a solution containing a reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative is obtained. This solution may be provided as it is to the preparation of the liquid crystal aligning agent, or the polymer contained in the solution may be provided to the preparation of the liquid crystal aligning agent, or after the isolated polymer is purified, the liquid crystal aligning agent is prepared. It can also be provided.

<(B) component>

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

(B) It is preferable that the crosslinking agent which is a component is a crosslinking agent which has the group which forms bridge | crosslinking with the heat-crosslinkable functional group 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 alkoxy methylation glycoluril, alkoxy methylation benzoguanamine, and alkoxy methylation melamine, are mentioned, for example.

Specific examples of the alkoxy methylated 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. As a commercial product, a compound such as Nippon Scitech Industries (formerly Mitsui Scitech Co., Ltd.) glycoluril compound (trade name: Cymel (registered trademark) 1170, PowderLink (registered trademark) 1174), methylated urea resin ( Product name: UFR (registered trademark) 65), butylated urea resin (brand name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd. (former Dai Nippon Inki Chemical Co., Ltd. )) Urea / formaldehyde-based resin (high-condensation type, brand name: Becamine (registered trademark) J-300S, copper P-955, copper N) and the like.

Tetramethoxymethylbenzoguanamine etc. are mentioned as a specific example of alkoxy methylation benzoguanamine. As a commercial product, manufactured by Nippon Scitech Industries (formerly Mitsui Scitech Co., Ltd.) (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nikarak (registered trademark) BX-4000 , Copper BX-37, copper BL-60, copper BX-55H) and the like.

As a specific example of the alkoxy methylated melamine, hexamethoxy methyl melamine etc. are mentioned, for example. As a commercial product, a methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, Copper 301, Copper 303, Copper 350), Butoxymethyl manufactured by Nippon Cytec Industries (formerly Mitsui Cytec Co., Ltd.) Type melamine compound (trade name: Mycoat (registered trademark) 506, copper 508), methoxymethyl type melamine compound made by Sanwa Chemical (trade name: Nikarac (registered trademark) MW-30, copper MW-22, copper MW) -11, copper MS-001, copper MX-002, copper MX-730, copper MX-750, copper MX-035), butoxymethyl type melamine compound (trade name: Nikarac (registered trademark) MX-45, copper MX -410, the same as MX-302).

Further, the hydrogen atom of the amino group may be a compound obtained by condensation of a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in U.S. Pat. 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) Etc. (former Mitsui Cytec Co., Ltd. product) etc. are mentioned.

Furthermore, as the crosslinking agent of component (B), hydroxymethyl groups such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide (i.e. Polymers prepared using acrylamide compounds or methacrylamide compounds substituted with methylol groups) or alkoxymethyl groups can also be used.

Such polymers include, for example, poly (N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, and copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate. Copolymers, copolymers of N-ethoxymethylmethacrylamide with benzyl methacrylate, and copolymers of N-butoxymethylacrylamide with benzylmethacrylate and 2-hydroxypropylmethacrylate. have.

Moreover, as such a polymer, a polymer having a polymerizable group containing an N-alkoxymethyl group and a C = C double bond can also be used.

As a polymerizable group containing a C = C double bond, an acryl group, a methacryl group, a vinyl group, an allyl group, a maleimide group, etc. are mentioned.

The method for obtaining the polymer as described above is not particularly limited. For example, an acrylic polymer having a specific functional group 1 is produced by a polymerization method such as radical polymerization in advance. Subsequently, by reacting this specific functional group 1 with a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound), a polymerizable group containing a C = C double bond can be introduced into the polymer (B) as a component. .

Here, the specific functional group 1 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 functional groups selected from these.

In the above-mentioned reaction, a preferable combination of the specific functional group 1 and the group involved in the reaction as a functional group of the specific compound is a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, a phenolic hydroxyl group and an epoxy group, a carboxyl group and an isocyanate group, Amino groups, isocyanate groups, hydroxy groups and acid chlorides. Furthermore, a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxy group and isocyanate ethyl methacrylate.

The weight average molecular weight of these polymers (polystyrene conversion value) is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

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

The content of the crosslinking agent of the component (B) in the cured film-forming composition of the present invention is preferably 1 part by mass to 500 parts by mass, more preferably 5 parts by mass based on 100 parts by mass of the polymer as the component (A). It is ~ 400 parts by mass. When the content of the crosslinking agent is excessive, the solvent resistance of the cured film obtained from the cured film forming composition decreases, and the liquid crystal alignment property decreases. On the other hand, when the content is excessive, liquid crystal orientation and storage stability may be lowered.

<(C) component>

The cured film forming composition of the present invention has, as component (C), at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group (hereinafter also referred to as a specific functional group 2). It may contain a polymer.

(C) As a component polymer, for example, acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone Polyols, polyalkyleneimines, polyallylamines, celluloses (cellulose or derivatives thereof), phenol novolac resins, melamine formaldehyde resins, etc., polymers having a straight-chain or branched structure, cyclic polymers such as cyclodextrins, etc. You can.

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

(C) The acrylic polymer which is a preferable example of the polymer of the component is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, or vinyl compound, and a monomer containing a monomer having a specific functional group 2 Or it may be a polymer obtained by polymerizing the mixture thereof, and the type of the backbone and side chains of the main chain of the polymer constituting the acrylic polymer is not particularly limited.

As a monomer having a specific functional group 2, 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 And a monomer having a group and a group represented by Formula 2 above.

As a monomer which has the above-mentioned polyethylene glycol ester group, H- (OCH ₂ CH ₂ ) n-OH monoacrylate or monomethacrylate is mentioned. The value of n is 2 to 50, preferably 2 to 10.

As the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms as described above, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2 -Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.

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

As a monomer which has the carboxyl group mentioned above, acrylic acid, methacrylic acid, and vinyl benzoic 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.

As a monomer which has the above-mentioned alkoxysilyl group in a side chain, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3- And methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.

Moreover, in this embodiment, when synthesize | combining the acrylic polymer which is an example of (C) component, among the groups represented by a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, unless the effect of this invention is impaired Monomers which do not have any can be used in combination.

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

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, and 2,2. , 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, Tetrahydrofurfurylacrylate, 3-methoxybutylacrylate, 2-methyl-2-adamantylacrylate, 2-propyl-2-adamantylacrylate, 8-methyl-8-tricyclodecylacrylate And, and 8-ethyl-8-tricyclodecylacrylate.

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, meth Methoxytriethylene 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.

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

As a styrene compound, styrene, methylstyrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

As a vinyl compound, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether etc. are mentioned, for example.

The amount of the monomer having a specific functional group 2 used to obtain the acrylic polymer as an example of the component (C) is preferably 2 mol% or more based on the total amount of the total monomers used to obtain the acrylic polymer as the component (C). When the monomer having the specific functional group 2 is less than 2 mol%, the solvent resistance of the resulting cured film tends to be insufficient.

(C) The method of obtaining an acrylic polymer which is an example of a component is not particularly limited, but, for example, a monomer containing a monomer having a specific functional group 2, a monomer having no specific functional group 2, a polymerization initiator, and the like coexist, if necessary. In the solvent, the obtained solution is obtained by polymerization at a temperature of 50 ° C to 110 ° C. In that case, the solvent used is not particularly limited as long as it dissolves the monomer having a specific functional group 2, the monomer having no specific functional group 2 used as necessary, a polymerization initiator, or the like. As a specific example, it describes in the term of [solvent] mentioned later.

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

In addition, a solution of the acrylic polymer, which is an example of the component (C) 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 is heat-dried and can be made into a powder of an acrylic polymer that is an example of the component (C). By the above-described operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer as an example of the component (C) can be removed, and as a result, a powder of the acrylic polymer as the example of the purified component (C) is obtained. If it is not possible to sufficiently purify in one operation, the obtained powder may be redissolved in a solvent, and the above-described operation may be repeated.

The acrylic polymer which is a preferable example of the component (C), preferably has a weight average molecular weight of 3000 to 200000, more preferably 4000 to 150000, and even more preferably 5000 to 100,000. If the weight average molecular weight is more than 200000, the solubility in the solvent may be lowered and the handling property may be deteriorated. If the weight average molecular weight is less than 3000, the solvent resistance becomes insufficient due to curing during thermal curing. It may fall. On the other hand, the weight average molecular weight is a value obtained by using polystyrene as standard data by gel permeation chromatography (GPC). Hereinafter, it is the same also in this specification.

Next, polyether polyols, which are preferable examples of the component (C), include polypropylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, polyhydric alcohols such as sorbitol, propylene oxide, polyethylene glycol, and polypropylene glycol. And those added. As a specific example of the polyether polyol, Adeka polyether P series, G series, EDP series, BPX series, FC series, CM series made by ADEKA, Uniox (registered trademark) HC-40, HC-60, ST- manufactured by Nichiyu Co., Ltd. 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 (registered trademark) LT-221, ST-221, OT-221 and the like.

As a preferred example of the component (C), polyols of ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc. are reacted with polycarboxylic acids such as adipic acid, sebacic acid, and isophthalic acid. And what you ordered. As a specific example of the polyester polyol, DIC polylite (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, Curaray 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 and the like.

The polycaprolactone polyol which is a preferable example of the component (C) includes those obtained by ring-opening polymerization of ε-caprolactone as a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. As specific examples of the polycaprolactone polyol, DIC-made polylite (trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel-proxel (trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.

As a polycarbonate polyol which is a preferable example of the component (C), those obtained by reacting polyhydric alcohols such as trimethylolpropane and ethylene glycol with diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Specific examples of the polycarbonate polyol include Proxel (trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, C-590, C-1050, C-2050, C-2090, C-3090, etc. have.

(C) As a preferable example of a component, celluloses, such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyalkyl celluloses, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, etc. Hydroxyalkyl alkylcelluloses and celluloses, and the like, and for example, hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose are preferred.

(C) Cyclodextrins, which are preferable examples of the components, include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl-γ -Methylated cyclodextrins such as cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxy Hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclo Dextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2 , 3- Hydroxypropyl, and the like -β- cyclodextrin, 2,3-di-hydroxypropyl -γ- cycloalkyl hydroxyalkyl cyclodextrin, such as cyclodextrin.

(C) As a preferable example of a component, a melamine formaldehyde resin is a resin obtained by polycondensing melamine and formaldehyde.

From the viewpoint of storage stability, it is preferable that the methylol group produced during polycondensation of melamine and formaldehyde is alkylated in the melamine formaldehyde resin of the component (C). (C) As a melamine formaldehyde resin of a component, the resin which has a unit structure represented by the following formula, for example is mentioned.

[Formula 6]

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

The method for obtaining the melamine formaldehyde resin of the component (C) is not particularly limited, but is generally synthesized by mixing melamine and formaldehyde, making it slightly alkaline using sodium carbonate or ammonia, and then heating at 60 ° C to 100 ° C. do. The methylol group can be alkoxylated by reacting with alcohol again.

The melamine formaldehyde resin of the component (C) preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and even more preferably 350 to 3500. If the weight average molecular weight is more than 5000, the solubility in the solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 250, the curing resistance is insufficient due to heat curing and solvent resistance In some cases, the improvement effect may not be sufficiently exhibited.

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

(C) As a preferable example of a component, a phenol novolak resin, For example, a phenol-formaldehyde polycondensate etc. are mentioned.

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

Moreover, in the cured film formation composition of this embodiment, (C) component may be a mixture of multiple types of polymers illustrated as (C) component.

The content in the case where the component (C) in the cured film-forming composition of the present invention is contained is preferably 400 parts by mass with respect to 100 parts by mass, which is the total amount of the crosslinking agent of the polymer (A) and the component (B). Hereinafter, it is more preferably 10 parts by mass to 380 parts by mass, and even more preferably 40 parts by mass to 360 parts by mass. When the content of the component (C) is excessive, the liquid crystal orientation tends to deteriorate.

<(D) Ingredient>

The cured film forming composition of the present invention may further contain a crosslinking catalyst as the component (D) in addition to the components (A) and (B).

(D) As a crosslinking catalyst which is a component, an acid or a thermal acid generator can be used conveniently, for example. This (D) component is effective in accelerating the thermosetting reaction of the cured film forming composition of the present invention.

(D) As a component, the sulfonic acid group containing compound, hydrochloric acid, or its salt is specifically, mentioned as said acid. The thermal acid generator is not particularly limited as long as it is a compound that thermally decomposes during heat treatment to generate an acid, that is, a compound that thermally decomposes at a temperature of 80 ° C to 250 ° C to generate an acid.

Specific examples of the acid include, for example, hydrochloric acid or a salt thereof; Methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-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 octasulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, or hydrates or salts thereof And the like.

Moreover, as a compound which generates an acid by heat, for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate, 1,2,3-phenylenetris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluene Butyl sulfonate ester, p-toluene sulfonate isobutyl ester, p-toluene sulfonate methyl ester, p-toluene sulfonate phenethyl ester, cyanomethyl p-toluene sulfonate, 2,2,2-trifluoroethyl p -Toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and further compounds represented by the following formula:

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

And the like.

The content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass, which is the total amount of the crosslinking agent of the polymer (A) and the component (B). , More preferably, it is 0.1 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass. (D) When content of a component is 0.01 mass part or more, sufficient thermosetting property and solvent resistance can be provided. However, when more than 20 parts by mass, the storage stability of the composition may be lowered.

<(E) component>

The present invention is a component (E), at least one group A selected from the group consisting of at least one polymerizable group, a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least 1 that reacts with the group A It may also contain compounds having dog groups. This acts as a component that improves the adhesion of the cured film to be formed (hereinafter also referred to as an adhesion improving component).

When using the cured film formed from the cured film forming composition of this embodiment containing the component (E) as an alignment material, the polymerizable functional group and alignment of the polymerizable liquid crystal are aligned so that the adhesion between the alignment material and the layer of the polymerizable liquid crystal is improved. The crosslinking site of the ash can be linked by covalent bonding. As a result, the retardation material of the present embodiment obtained by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under conditions of high temperature and high quality, and can exhibit high durability against peeling and the like. .

As the component (E), monomers and polymers having groups selected from hydroxy groups and N-alkoxymethyl groups and polymerizable groups are preferred.

Examples of the component (E) include a compound having a hydroxy group and a (meth) acrylic group, a compound having an N-alkoxymethyl group and a (meth) acrylic group, a polymer having an N-alkoxymethyl group and a (meth) acrylic group, and the like. Hereinafter, specific examples are shown.

(E) As an example of a component, the polyfunctional acrylate containing a hydroxyl group (Hereinafter, it is also called a hydroxy group containing polyfunctional acrylate.) Is mentioned.

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

(E) As an example of a component, the compound which has 1 acrylic group and 1 or more hydroxyl group is also mentioned. Preferred examples of such a compound having one acrylic group and one or more hydroxy groups are given. In addition, the compound of (E) component is not limited to the following compound example.

[Formula 13]

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

As a polymerizable group containing a C = C double bond, an acryl group, a methacryl group, a vinyl group, an allyl group, a maleimide group, etc. are mentioned.

N, the nitrogen atom of the N-alkoxy methyl group, is bonded to the adjacent position of the nitrogen atom of the amide, the nitrogen atom of the thioamide, the nitrogen atom of the urea, the nitrogen atom of the thiourea, the nitrogen atom of the urethane, the nitrogen atom of the nitrogen-containing heterocycle Nitrogen atoms, and the like. Therefore, as the N-alkoxy methyl group, the nitrogen atom of the amide, the nitrogen atom of the thioamide, the nitrogen atom of the urea, the nitrogen atom of the thiourea, the nitrogen atom of the urethane, and the nitrogen atom bound to the nitrogen atom of the nitrogen-containing heterocyclic ring The structure which the alkoxy methyl group couple | bonded with the nitrogen atom selected from etc. is mentioned.

(E) As long as it has what has the said group as a component, Preferably, the compound represented by following formula (X1) is mentioned, for example.

[Formula 14]

(Wherein, R ³¹ represents a hydrogen atom or a methyl group, R ³² represents a hydrogen atom, or a straight-chain or branched alkyl group having 1 to 10 carbon atoms)

As said alkyl group, For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methyl- n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl -n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl -n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n- Propyl group, 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, etc. are mentioned.

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

(E) As another aspect of the compound which has a polymerizable group containing a C = C double bond of a component and an N-alkoxy methyl group, Preferably, the compound represented by following formula (X2) is mentioned. .

[Formula 15]

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group.

R ⁵² represents an alkyl group having 2 to 20 carbon atoms, a monovalent aliphatic ring group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and may contain an ether bond in the structure. .

R ⁵³ represents a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or a divalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and is an ether bond in the structure. It may contain.

R ⁵⁴ is a straight or branched chain divalent to divalent to hexavalent aliphatic group having 1 to 20 carbon atoms, divalent to hexavalent aliphatic group having 5 to 6 carbon atoms, or divalent containing an aliphatic ring having 5 to 6 carbon atoms. It represents a 9-valent aliphatic group, and a methylene group of one of these groups or a plurality of non-adjacent methylene groups may be substituted with ether bonds.

Z is> NCOO-, or -OCON <(where "-" indicates that there is one bonding hand. In addition, ">" and "<" indicates that there are two bonding hands, and alkoxy is added to any one bonding hand. Methyl group (that is, -OR52 group).

r is a natural number of 2 or more and 9 or less.

As a specific example of the alkylene group having 2 to 20 carbon atoms in the definition of R ⁵³ , a divalent group in which one hydrogen atom is further removed from an alkyl group having 2 to 20 carbon atoms is mentioned.

Moreover, as a specific example of the divalent to 9-valent aliphatic group of 1 to 20 carbon atoms in the definition of R ⁵⁴ , divalent to 9 of 1 to 8 hydrogen atoms further removed from an alkyl group of 1 to 20 carbon atoms. There is a false flag.

The alkyl group having 1 carbon atom is a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and 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-pentade Real group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-ecosyl group, cyclopentyl group, cyclohexyl group, one of them or up to 20 carbon atoms Examples include a group bonded in the range, a group in which methylene of one of these groups or a plurality of non-adjacent methylene groups are substituted with ether bonds.

Of 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, particularly preferably from the viewpoint of availability of raw materials.

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 and the methyl group in the definition of R ⁵³ . Among them, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, ethyl group, n-propyl group or n-butyl group is particularly preferable.

As r, a natural number of 2 or more and 9 or less may be mentioned, and 2 to 6 is preferable.

The content of the component (E) in the cured film forming composition of the embodiment of the present invention is preferably 1 part by mass to 100 parts by mass, which is the total amount of the crosslinking agent of the polymer (A) and the component (B) It is 100 parts by mass, and more preferably 5 parts by mass to 70 parts by mass. (E) When content of a component is 1 mass part or more, sufficient adhesiveness can be provided to the cured film formed. However, when it is more than 100 parts by mass, the liquid crystal orientation tends to deteriorate.

Moreover, in the cured film forming composition of this embodiment, (E) component may be a mixture of multiple types of the compound of (E) component.

<Solvent>

The cured film forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent to be used at that time should be able to dissolve (A) component, (B) component and (C) component, (D) component, (E) component and / or other additives described later, if necessary. And the structure and the like are not particularly limited.

As a specific example of a solvent, for example, 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-pentane On, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, pyruvate Ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl methyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. .

In the case of using the cured film forming composition of the present invention and forming a cured film on a resin film to prepare 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, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, etc. It is preferable from a point.

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

<Other additives>

In addition, the cured film forming composition of the present invention, as long as the effects of the present invention are not impaired, adhesion enhancers, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, preservative stabilizers, antifoaming agents, oxidation Antioxidants and the like.

<Preparation of cured film forming composition>

The cured film-forming composition of the present invention contains a polymer of component (A) and a crosslinking agent of component (B), a polymer of component (C), a crosslinking catalyst of component (D), and a component (E) adhesion promoter as necessary. And, it is a composition that may further contain other additives as long as the effects of the present invention are not impaired. And usually, they are used in the form of a solution dissolved in a solvent.

Preferred examples of the cured film forming composition of the present invention are as follows.

[1]: A cured film forming composition containing 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A) and (A).

[2]: The total amount of the crosslinking agent of the (B) component and the (A) component polymer and (B) component, based on 100 parts by mass of the (A) component and (A) component, Cured film forming composition containing 1-400 mass parts (C) component with respect to 100 mass parts.

[3]: A cured film forming composition containing 1 part by mass to 500 parts by mass of (B) component and a solvent based on 100 parts by mass of component (A) and component (A).

[4]: 100 parts by mass based on 100 parts by mass of (A) component and (A) component, and 1 part by mass to 500 parts by mass of (B) component, (A) component polymer, and (B) component total amount of crosslinking agent. Cured film forming composition containing 1-400 mass parts (C) component with respect to part, and a solvent.

[5]: 100 parts by mass based on 100 parts by mass of (A) component and (A) component, and 1 part by mass to 500 parts by mass of (B) component, (A) component polymer, and (B) component total amount of crosslinking agent. 1 part to 400 parts by mass of (C) component, (A) component and (B) component containing 100 parts by mass of the total amount of the crosslinking agent, 0.01 parts by mass to 20 parts by mass of (D) component, containing a solvent Cured film forming composition.

[6]: 100 parts by mass based on 100 parts by mass of (A) component and (A) component, and 1 part by mass to 500 parts by mass of (B) component, (A) component polymer, and (B) component total amount of crosslinking agent. 1 part to 400 parts by mass of (C) component, (A) component, and (B) component to 100 parts by mass of the total amount of the crosslinking agent, 0.01 parts by mass to 20 parts by mass (D) component, (A) component The cured film forming composition containing 1 mass part-100 mass parts (E) component, and a solvent with respect to 100 mass parts which is the total amount of the crosslinking agent of a phosphorus polymer and (B) component.

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

The ratio of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent, but is 1% by mass to 60% by mass, preferably 2% by mass to 50% It is mass%, More preferably, it is 2 mass%-20 mass%. Here, solid content means the thing remove | excluding the solvent from the whole component of the cured film formation composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, (B) component, furthermore (C) component, (D) component, (E) component, etc. are mixed in the solution of (A) component melt | dissolved in the solvent at a predetermined ratio, and uniform The method of making it into one solution, or in the appropriate step of this preparation method, the method of adding and mixing other additives as needed is mentioned.

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

Moreover, it is preferable to use the solution of the prepared cured film forming composition after filtering using a filter or the like having a pore diameter of about 0.2 µm.

<Cured film, alignment material and retardation material>

The solution of the cured film forming composition of the present invention is 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, glass substrate, quartz substrate) , ITO substrate, etc.) or film substrate (for example, 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., coated with bar coat, rotating coating, spill coating, roll coating, slit coating, slit rotating coating, inkjet coating, printing, etc. to form a coating film Then, by heating and drying in a hot plate or an oven, a cured film can be formed. This cured film can be applied as an alignment material as it is.

Under the conditions of heating and drying, the crosslinking reaction by a crosslinking agent may be carried out so that the components of the cured film (orientation material) do not elute in the polymerizable liquid crystal solution applied thereon, for example, the temperature is 60 ° C to 200 A heating temperature and a heating time suitably selected from the range of ℃ and time from 0.4 minutes to 60 minutes are employed. The heating temperature and the heating time are preferably 70 ° C to 160 ° C and 0.5 minutes to 10 minutes.

The film thickness of the cured film (orientation 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, and electrical properties of the substrate to be used.

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 orientation can be coated on the alignment material and aligned on the alignment material. Then, the retardation material in the aligned state can be cured as it is to form a retardation material as a layer having optical anisotropy. In addition, when the substrate forming the alignment material is a film, it is useful as a retardation film.

Further, using two substrates having the alignment material of the present invention formed as described above, and interposing spacers to align the alignment materials on both substrates via spacers, and then injecting liquid crystal between these substrates, thereby liquid crystal It can also be set as an oriented liquid crystal display element.

In this way, the cured film forming composition of the present invention can be suitably used for the production of various phase difference materials (phase difference films), liquid crystal display devices, and the like.

Example

Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not limited to these.

[Medicine symbol used in Examples]

The meaning of the weak symbol used in the following examples is as follows.

<Raw material>

GMA: glycidyl methacrylate

AIBN: α, α’-azobisisobutyronitrile

BMAA: N-butoxymethylacrylamide

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

<Cinnamic acid compound having a polymerizable group>

CIN1: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid

[Formula 16]

CIN2: 4- (3-methacryloxypropyl-1-oxy) cinnamic acid

[Formula 17]

CIN3: 4- (6-acryloxyhexyl-1-oxy) cinnamic acid

[Formula 18]

<Cinnamic acid compound not having a polymerizable group>

CIN4: 4-methoxy cinnamic acid

[Formula 19]

<Component B>

HMM: Melamine crosslinking agent represented by the following structural formula [CYMEL (registered trademark) 303 (Mitsui Cytec Co., Ltd.)]

[Formula 20]

<D ingredient>

PTSA: p-toluene sulfonic acid monohydrate

<E component>

E-1: Compound having an N-alkoxymethyl group and an acrylic group represented by the following structural formula

[Formula 21]

<Solvent>

Each resin composition of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM) was used as the solvent.

<Measurement of molecular weight of polymer>

The molecular weight of the acrylic copolymer in the polymerization example is a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and a column (KD-803, KD-805) manufactured by Shodex. Was measured.

On the other hand, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene conversion values.

Column temperature: 40 ℃

Eluent: Tetrahydrofuran

Flow rate: 1.0 mL / min

Standard sample for calibration calibration: Standard polystyrene manufactured by Showa Denko Corporation (molecular weights about 197,000, 55,100, 12,800, 3,950, 1,260, 580).

<Synthesis of component A>

<Polymerization Example 1>

Acrylic polymer solution was obtained by dissolving 15.0 g of GMA and 0.5 g of AIBN as a polymerization catalyst in 46.4 g of tetrahydrofuran and reacting for 20 hours under reflux under heating. The obtained acrylic copolymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, followed by filtration and drying under reduced pressure to obtain an acrylic polymer (P1) having an epoxy group. Mn of the obtained acrylic polymer was 25,000 and Mw was 10,000.

<Synthesis Example 1>

Dissolve the acrylic polymer (P1) having the epoxy group obtained in the polymerization example 1 (P1) 5.2 g, CIN1 12.0 g, 0.1 g ethyl triphenylphosphonium bromide as a reaction catalyst, and 0.2 g dibutylhydroxytoluene as a polymerization inhibitor in PM 70.0 g , And reacted at 100 ° C for 20 hours. This solution was slowly added dropwise to 1000 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-1). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 2>

The acrylic polymer (P1) having the epoxy group obtained in the polymerization example 1, 5.2g, CIN2 11.0g, ethyltriphenylphosphonium bromide 0.1g as a reaction catalyst, and 0.2g dibutylhydroxytoluene as a polymerization inhibitor were dissolved in PM 70.0g. , And reacted at 100 ° C for 20 hours. This solution was slowly added dropwise to 1000 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-2). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 3>

Dissolve the acrylic polymer (P1) having the epoxy group obtained in the polymerization example 1 (P1) 5.2 g, CIN3 12.0 g, 0.1 g of ethyl triphenylphosphonium bromide as a reaction catalyst, and 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor in PM 70.0 g. , And reacted at 100 ° C for 20 hours. The solution was slowly added dropwise to 1000 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-3). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 4>

Phenolic novolac-type epoxy resin N-775 (DIC Corporation EPICLON series) 5.7g, CIN1 11.0g, reaction catalyst ethyl triphenylphosphonium bromide 0.2g, polymerization inhibitor dibutylhydroxytoluene 0.2g PM It was dissolved in 40.0 g and reacted at 100 ° C for 20 hours. This solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-4). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 5>

Acrylic polymer (P1) having an epoxy group obtained in polymerization example 1 5.2g, CIN1 10.0g, CIN4 2.0g, ethyl triphenylphosphonium bromide 0.1g as a reaction catalyst, 0.2g dibutylhydroxytoluene as a polymerization inhibitor PM 70.0 It was dissolved in g and reacted at 100 ° C for 20 hours. The solution was slowly added dropwise to 1000 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-5). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 6>

Acrylic polymer (P1) having an epoxy group obtained in Polymerization Example 1 (P1) 5.2g, CIN4 6.5g, ethyl triphenylphosphonium bromide 0.1g as a reaction catalyst was dissolved in PM 48.0g, and reacted at 100 ℃ for 20 hours. This solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-6). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 7>

Phenolic novolac-type epoxy resin N-775 (DIC Corporation EPICLON series) 5.3g, CIN4 5.0g, ethyltriphenylphosphonium bromide 0.2g as a reaction catalyst was dissolved in PM 25.0g and reacted at 100 ° C for 20 hours Ordered. This solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-7). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis of B component>

<Polymerization Example 2>

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. Mn of the obtained acrylic polymer was 2,700 and Mw was 3,900. The acrylic polymer solution was slowly added dropwise to 2000.0 g of hexane to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PB-1).

<Synthesis of C component>

<Polymerization Example 3>

An acrylic copolymer solution was obtained by dissolving 30.0 g of MMA, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 146.0 g of PM and reacting at 80 ° C for 20 hours. The acrylic copolymer solution was slowly added dropwise to 1000.0 g of hexane to precipitate a solid, and the acrylic copolymer (PC-1) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic copolymer was 18,000, and Mw was 32,800.

<Example, Comparative Example>

The cured film forming compositions of Examples and Comparative Examples were prepared with the compositions shown in Table 1. Next, a cured film was formed using each retardation-forming composition, and the orientation and adhesion were evaluated for each of the obtained cured films.

[Table 1]

[Evaluation of orientation]

Each cured film forming composition of Examples and Comparative Examples was coated on a COP film subjected to ozone treatment to a Wet film thickness of 4 μm using a bar coater. Each was heated and dried in a thermal cycle oven at a temperature of 110 ° C. for 60 seconds, and cured films were respectively formed on the COP film. Each of the cured films was irradiated vertically with a linear polarization of 313 nm at an exposure amount of 10 mJ / cm ² to form an alignment material. On the alignment material on the COP film, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was coated with a Wet film thickness of 6 μm using a bar coater. This coating film was exposed at 300 mJ / cm ² to prepare a phase difference material. The phase difference material on the produced substrate was sandwiched by a pair of polarizing plates, and the state of expression of the phase difference characteristics in the phase difference material was observed, and the phase difference was expressed without defects. ”Column. The evaluation results are summarized in Table 2 later.

[Evaluation of adhesion]

Each cured film forming composition of Examples and Comparative Examples was coated on a COP film subjected to ozone treatment to a Wet film thickness of 4 μm using a bar coater. Each was heated and dried in a thermal cycle oven at a temperature of 110 ° C. for 60 seconds, and cured films were respectively formed on the COP film. Each of the cured films was irradiated vertically with a linear polarization of 313 nm at an exposure amount of 10 mJ / cm ² to form an alignment material. On the alignment material on the COP film, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was coated with a Wet film thickness of 6 μm using a bar coater. This coating film was exposed at 300 mJ / cm ² to prepare a phase difference material. A sheath was placed in the phase difference material with a cutter knife so as to be 10 × 10 squares with a width of 1 mm. A cellophane tape peeling test was conducted on the sheath using scotch tape. The evaluation result was set to "adhesiveness", and those that remained without peeling off all 100 spaces were designated as ○ and those that were peeled off even at one space were set to x. The evaluation results are summarized in Table 2 later.

[Table 2]

As shown in Table 2, the alignment material obtained using the cured film-forming composition of Examples showed good alignment and adhesion.

On the other hand, although the orientation material obtained using the cured film formation composition of a comparative example showed favorable orientation property, adhesiveness was not obtained.

Industrial availability

The cured film forming composition according to the present invention is very useful as a material for forming an alignment material for forming an optically anisotropic film provided inside or outside a liquid crystal alignment film of a liquid crystal display device or a liquid crystal display device. It is suitable as a material for retardation of a circular polarizing plate used as an antireflection film for LCDs or organic EL displays.

Claims (14)

(A) A reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a cured film forming composition containing a crosslinking agent. According to claim 1,
The group containing the polymerizable double bond is a (meth) acryloyl group cured film forming composition. The method according to claim 1 or 2,
The cinnamic acid derivative having a group containing a polymerizable double bond is a compound represented by the following formula (1), a cured film forming composition.
[Formula 1]

In Formula (1), A ¹ and A ² each independently represent a hydrogen atom or a methyl group,
R ¹ is the following formula (c-2)
[Formula 2]

(In the formula (c-2), the broken line represents a bond, R ¹⁰¹ represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms in the alkylene group may be substituted with a fluorine atom or an organic group. Further, -CH ₂ CH ₂ -in R ¹⁰¹ may be substituted with -CH = CH-, and further, when any one of the following groups is not adjacent to each other, -O-, -NHCO It may be substituted with a group selected from the group consisting of-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, and M ¹ represents a hydrogen atom or a methyl group.) Represents the displayed group,
R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group,
R ³ represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-,
R ⁴ to R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, And a substituent selected from the group consisting of nitro groups,
Further, R ² , R ³ and R ⁴ or R ² , R ³ and R ⁶ may be united to form an aromatic group,
n is an integer from 0 to 3.) The method according to any one of claims 1 to 3,
(B) The cured film formation composition whose crosslinking agent of a component is a crosslinking agent which has a methylol group or an alkoxymethyl group. The method according to any one of claims 1 to 4,
(C) A cured film forming composition further comprising a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. The method according to any one of claims 1 to 5,
(D) Cured film forming composition further containing a crosslinking catalyst. The method according to any one of claims 1 to 6,
(E) Contains a compound having at least one polymer A, at least one group A selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least one group reacting with the group A Cured film forming composition. The method according to any one of claims 1 to 7,
(A) The cured film formation composition containing 1 mass part-500 mass parts (B) component based on 100 mass parts of components. The method according to any one of claims 5 to 8,
The cured film formation composition containing 1 mass part-400 mass parts (C) component with respect to 100 mass parts which is the total amount of the crosslinking agent of (A) component and (B) component. The method according to any one of claims 6 to 9,
The cured film formation composition containing 0.01 mass part-20 mass parts (D) component with respect to 100 mass parts which is the total amount of the crosslinking agent of (A) component and (B) component. The method according to any one of claims 7 to 10,
The cured film formation composition containing 1 mass part-100 mass parts (E) component with respect to 100 mass parts which is the total amount of the crosslinking agent of (A) component and (B) component. A cured film obtained from the cured film forming composition according to any one of claims 1 to 11. It is obtained from the cured film formation composition in any one of Claims 1-11, The orientation material characterized by the above-mentioned. It is formed using the cured film obtained from the cured film forming composition in any one of Claims 1-11, The retardation material characterized by the above-mentioned.