WO2018181350A1 - Cured film–forming composition, alignment material, and phase difference material - Google Patents

Abstract

[Problem] To provide a cured film–forming composition for forming a cured film which exhibits excellent liquid crystal alignment properties and light transmissivity when used as an alignment material with a layer of a polymerizable liquid crystal disposed thereupon. [Solution] A cured film–forming composition containing (A) a polymer obtained using a monomer, the monomer being a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by formula (1), and (B) a crosslinking agent; an alignment material characterized by being obtained using the composition; and a phase difference material characterized by being obtained using the composition. (In formula (1): A1 and A2 represent a hydrogen atom or a methyl group; R1 represents a hydrogen atom, a halogen atom, or the like; R2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group; R3 is a single bond, an oxygen atom, or the like; R4 to R7 are each independently a hydrogen atom, a halogen atom, or the like; and n is an integer from 0 to 3.)

Description

Cured film forming composition, alignment material and retardation material

The present invention relates to a cured film forming composition that can be used as a liquid crystal aligning agent for photo-alignment for aligning liquid crystal molecules, an alignment material, and a retardation material. In particular, the present invention is useful for producing a patterned retardation material used in a circularly polarized glasses type 3D display and a retardation material used in a circularly polarizing plate used as an antireflection film of an organic EL display. The present invention relates to a cured film forming composition, an alignment material, and a retardation material that can be used as a liquid crystal alignment agent for photo-alignment.

In the case of a circularly polarized glasses type 3D display, a retardation material is usually disposed on a display element such as a liquid crystal panel. In this retardation material, a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged, and a patterned retardation material is formed. Hereinafter, in the present specification, a retardation material patterned so as 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. Optical patterning of a retardation material made of a polymerizable liquid crystal utilizes a photo-alignment technique known for forming 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 types of polarized light having different polarization directions are irradiated on the coating film. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. A solution-like retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.

The anti-reflective film of the organic EL display is composed of a linear polarizing plate and a quarter-wave retardation plate, converts external light directed to the panel surface of the image display panel into linear polarized light by the linear polarizing plate, and continues to the quarter wavelength. It is converted into circularly polarized light by the phase difference plate. Here, the extraneous light by the circularly polarized light is reflected by the surface of the image display panel or the like, but the rotation direction of the polarization plane is reversed during the reflection. As a result, contrary to the arrival time, this reflected light is converted from the quarter-wave retardation plate into linearly polarized light in the direction shielded by the linear polarizing plate, and then shielded by the subsequent linear polarizing plate, As a result, the emission to the outside is remarkably suppressed.

Regarding this 1/4 wavelength phase difference plate, Patent Document 2 discloses that this optical film has a reverse dispersion characteristic by configuring a 1/4 wavelength phase difference plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate. Has been proposed. In the case of this method, an optical film can be formed with reverse dispersion characteristics using a liquid crystal material with positive dispersion characteristics in a wide wavelength band used for displaying a color image.

In recent years, as liquid crystal materials applicable to the retardation layer, those having reverse dispersion characteristics have been proposed (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 combining two half-wave plates and a quarter-wave plate to form a quarter-wave retardation plate. It is possible to achieve an optical film capable of ensuring a desired phase difference in a wide wavelength band with a simple configuration.

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

In the formation of alignment materials using the photo-alignment method, acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chain are known as usable photo-alignment materials. These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) when irradiated with polarized UV light (see Patent Documents 5 to 7).

Also, the alignment layer is required to have solvent resistance in addition to the liquid crystal alignment ability. For example, the alignment layer may be exposed to heat or a solvent in the manufacturing process of the retardation material. When the alignment layer is exposed to a solvent, the liquid crystal alignment ability may be significantly reduced.

Therefore, for example, in Patent Document 8, in order to obtain stable liquid crystal alignment ability, a liquid crystal aligning agent containing a polymer component having a structure capable of crosslinking reaction by light and a structure crosslinked by heat, and light. A liquid crystal aligning agent containing a polymer component having a structure capable of crosslinking reaction and a compound having a structure crosslinked by heat has been proposed.

JP 2005-49865 A Japanese Patent Laid-Open No. 10-68816 U.S. Pat. No. 8,119,026 JP 2009-179563 A Japanese Patent No. 3611342 JP 2009-058584 A JP-T-2001-517719 Japanese Patent No. 4207430

As described above, the retardation material is formed by laminating a cured polymerizable liquid crystal layer on a photo-alignment film that is an alignment material. Therefore, it is necessary to develop an alignment material that can achieve both excellent liquid crystal alignment and solvent resistance.

However, according to the study of the present inventor, it has been found that an acrylic resin having a photodimerization site such as a cinnamoyl group and a chalcone group in the side chain cannot obtain sufficient characteristics when applied to the formation of a retardation material. It was issued. In particular, in order to form an alignment material by irradiating polarized UV to these resins and to produce a retardation material composed of a polymerizable liquid crystal using the alignment material, a large amount of polarized UV exposure is required. The polarized UV exposure amount is much larger than the polarized UV exposure amount (for example, about 30 mJ / cm 2) sufficient to align the liquid crystal for a normal liquid crystal panel.

The reason for increasing the amount of polarized UV exposure is that, in the case of retardation material formation, unlike liquid crystals for liquid crystal panels, polymerizable liquid crystals are used in the state of solution and applied onto the alignment material. Yes.

When an alignment material is formed using an acrylic resin having a photodimerization site such as a cinnamoyl group in the side chain, and the polymerizable liquid crystal is to be aligned, the acrylic resin is subjected to photocrosslinking by a photodimerization reaction. . And it is necessary to irradiate polarized light with many exposure amounts until resistance to the polymerizable liquid crystal solution is developed. In order to align the liquid crystal of the liquid crystal panel, it is usually only necessary to dimerize only the surface of the photo-alignment alignment material. However, if a conventional material such as the above-mentioned acrylic resin is used to cause the alignment material to exhibit solvent resistance, it is necessary to cause the alignment material to react, and a larger amount of exposure is required. As a result, there is a problem that the orientation sensitivity of the conventional material becomes very small.

In addition, a technique of adding a crosslinking agent in order to develop such solvent resistance in the above-described conventional resin is known. However, after the thermosetting reaction with the crosslinking agent, a three-dimensional structure is formed inside the formed coating film, and the photoreactivity is lowered. That is, the orientation sensitivity is greatly reduced, and the desired effect is not obtained even when a conventional material is added with a crosslinking agent.

From the above, a photo-alignment technique that can improve the alignment sensitivity of the alignment material and reduce the polarized UV exposure amount, and a cured film forming composition that can be used as a liquid crystal aligning agent for photo-alignment used in the formation of the alignment material It has been. And the technique which can provide a phase difference material with high efficiency is calculated | required.

The object of the present invention has been made based on the above knowledge and examination results. That is, an object of the present invention is to form a cured film that can be used as a liquid crystal aligning agent for photo-alignment for providing an alignment material that has excellent solvent resistance and can align a polymerizable liquid crystal with high sensitivity. It is to provide a composition.

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

As a result of intensive studies to achieve the above object, the present inventors have (A) a reaction product of a monomer having an epoxy group and a specific cinnamic acid derivative, and (B) a cured film based on a crosslinking agent. By selecting a forming composition, it was found that a cured film (alignment material) having excellent solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity could be formed, and the present invention was completed.

That is, the present invention as a first aspect,
(A) a polymer obtained by using a monomer that is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the following formula (1):

(In Formula (1), A ¹ and A ² each independently represent a hydrogen atom or a methyl group, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Haloalkyl groups, alkoxy groups having 1 to 6 carbon atoms, haloalkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, halocycloalkyl groups having 3 to 8 carbon atoms, carbon, carbon An alkenyl group having 2 to 6 atoms, a haloalkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, a halocycloalkenyl group having 3 to 8 carbon atoms, and 2 to 6 carbon atoms Alkynyl group, haloalkynyl group having 2 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, haloalkoxy group having 1 to 6 carbon atoms, (alkyl having 1 to 6 carbon atoms) carbonyl group, (carbon C with 1-6 atoms (Alkyl) carbonyl group, (alkoxy having 1 to 6 carbon atoms) carbonyl group, (haloalkoxy having 1 to 6 carbon atoms) carbonyl group, (alkylamino having 1 to 6 carbon atoms) carbonyl group, (number of carbon atoms) 1 to 6 haloalkyl) aminocarbonyl group, di (alkyl having 1 to 6 carbon atoms) aminocarbonyl group, a substituent selected from the group consisting of cyano group and nitro group, R ² is a divalent aromatic group R 2 represents a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, R ³ represents a single bond, an oxygen atom, —COO— or —OCO—, and 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, or a haloalkoxy group having 1 to 6 carbon atoms. Group, cyano , And it represents a substituent selected from the group consisting of nitro group, n is an integer of 0-3.)
(B) A cured film forming composition containing a crosslinking agent.
As a 2nd viewpoint, it is related with the cured film formation composition as described in a 1st viewpoint whose crosslinking agent of (B) component is a crosslinking agent which has a methylol group or an alkoxymethyl group.
As a third aspect, (C) described in the first aspect or the second aspect further containing 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 present invention relates to a cured film forming composition.
As a 4th viewpoint, it is related with the cured film formation composition as described in any one of the 1st viewpoint thru | or the 3rd viewpoint which further contains (D) a crosslinking catalyst.
As a fifth aspect, (E) reaction with one or more polymerizable groups and 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 the group A It relates to the cured film forming composition as described in any one of the 1st viewpoint thru | or a 4th viewpoint containing the compound which has at least 1 group to do.
As a sixth aspect, the cured film formation according to any one of the first aspect to the fifth aspect containing 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A) Relates to the composition.
As a seventh aspect, from the third aspect to the sixth aspect, containing 1 part by mass to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B). It is related with the cured film formation composition as described in any one.
As an eighth aspect, the fourth aspect to the seventh aspect contain the component (D) in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the crosslinking agents of the components (A) and (B) The cured film forming composition according to any one of the aspects.
As a ninth aspect, the fourth aspect to the eighth aspect containing the component (E) in an amount of 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B) It is related with the cured film formation composition as described in any one.
As a tenth aspect, the present invention relates to a cured film obtained by curing the cured film-forming composition according to any one of the first to ninth aspects.
An eleventh aspect relates to an alignment material obtained by curing the cured film forming composition according to any one of the first to ninth aspects.
As a twelfth aspect, the present invention relates to a retardation material characterized by being formed using a cured film obtained from the cured film forming composition according to any one of the first aspect to the ninth aspect.

ADVANTAGE OF THE INVENTION According to this invention, it can provide the cured film which has the outstanding solvent resistance, can align a polymerizable liquid crystal with high sensitivity, and a cured film formation composition suitable for the formation.
ADVANTAGE OF THE INVENTION According to this invention, the phase difference material in which the orientation material excellent in liquid crystal orientation and light transmittance and high-precision optical patterning are possible can be provided.

<Curing film forming composition>
The cured film forming composition of the present invention comprises (A) a polymer obtained by using a monomer that is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1), and (B ) Contains a crosslinking agent. In addition to the components (A) and (B), the cured film forming composition of the present invention further comprises a group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group as the component (C). It is also possible to contain a polymer having at least one group selected from Furthermore, a crosslinking catalyst can also be contained as (D) component. Furthermore, as the component (E), at least one group A selected from the group consisting of one or more polymerizable groups, a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least reacts with the group A Compounds having one group can be contained. And as long as the effect of this invention is not impaired, another additive can be contained.
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 obtained by using a monomer that is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1). It is a coalescence.

<Monomer having an epoxy group>
Specific examples of the polymerizable unsaturated compound (monomer) having an epoxy group used for the reaction with the cinnamic acid derivative represented by the above formula (1) in the present invention include, for example, glycidyl acrylate, glycidyl methacrylate, α- Glycidyl ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-acrylic acid Mention of epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Can do.

<Cinnamic acid derivative having a carboxyl group>
Examples of the cinnamic acid derivative having a carboxyl group include compounds represented by the above formula (1).

Examples of the halogen atom in the above formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the present specification, the notation “halo” also represents these halogen atoms.

The notation of an alkyl group having carbon atoms a to b in the above formula (1) represents a linear or branched hydrocarbon group having carbon atoms of a to b, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1 Specific examples include dimethylbutyl group, 1,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. Be-option.

The notation of the haloalkyl group having carbon atoms a to b in the above formula (1) is a straight chain comprising a to b carbon atoms, in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted with a halogen atom. Alternatively, it represents a branched hydrocarbon group, and when substituted with two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, chlorofluoromethyl group, dichloromethyl group, bromofluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group, dichlorofluoromethyl group, trichloromethyl Group, bromodifluoromethyl group, bromochlorofluoromethyl group, dibromofluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2-chloro-2-fluoroethyl Group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2 -Fluoroethyl group, 2,2,2-trichloroethyl group, 2 Bromo-2,2-difluoroethyl group, 2-bromo-2-chloro-2-fluoroethyl group, 2-bromo-2,2-dichloroethyl group, 1,1,2,2-tetrafluoroethyl group, penta Fluoroethyl group, 1-chloro-1,2,2,2-tetrafluoroethyl group, 2-chloro-1,1,2,2-tetrafluoroethyl group, 1,2-dichloro-1,2,2- Trifluoroethyl group, 2-bromo-1,1,2,2-tetrafluoroethyl group, 2-fluoropropyl group, 2-chloropropyl group, 2-bromopropyl group, 2-chloro-2-fluoropropyl group, 2,3-dichloropropyl group, 2-bromo-3-fluoropropyl group, 3-bromo-2-chloropropyl group, 2,3-dibromopropyl group, 3,3,3-trifluoropropyl group, 3-butyl Mo-3,3-difluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2-chloro-3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoro Propyl group, 1,1,2,3,3,3-hexafluoropropyl group, heptafluoropropyl group, 2,3-dichloro-1,1,2,3,3-pentafluoropropyl group, 2-fluoro- 1-methylethyl group, 2-chloro-1-methylethyl group, 2-bromo-1-methylethyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, 1,2,2 , 2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,2,3,3,4,4-hexafluorobutyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3,3,4,4,4-hep Tafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, nonafluorobutyl group, 4-chloro-1,1,2,2,3,3,4,4 -Octafluorobutyl group, 2-fluoro-2-methylpropyl group, 2-chloro-1,1-dimethylethyl group, 2-bromo-1,1-dimethylethyl group, 5-chloro-2,2,3, Specific examples include a 4,4,5,5-heptafluoropentyl group, a tridecafluorohexyl group, and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of the cycloalkyl group having a carbon number of a to b in the above formula (1) represents a cyclic hydrocarbon group having a carbon number of a to b, a monocyclic ring having 3 to 6 members, A complex ring structure can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms. For example, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2- Specific examples include methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo [2.2.1] heptan-2-yl group, and the like. Each of which is selected for each specified number of carbon atoms.

In the above formula (1), the description of the halocycloalkyl group having a carbon number of a to b is a cyclic group in which the hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom and having a carbon number of a to b. And can form a monocyclic or complex ring structure of 3 to 6 membered rings. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, They may be both, and when they are substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other. For example, 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2,2-dichloro-1-methyl Cyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group , 4- (trifluoromethyl) cyclohexyl group and the like are listed as specific examples, and each is selected within the range of the designated number of carbon atoms.

In the above formula (1), the alkenyl group having a carbon number of a to b is linear or branched having a carbon number of a to b, and one or two or more carbon atoms in the molecule. Represents an unsaturated hydrocarbon group having a heavy bond, for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2 -Propenyl group, 2-pentenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2-ethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 2-hexenyl Group, 2-methyl-2-pentenyl group, 2,4-dimethyl-2,6-heptadienyl group, 3,7-dimethyl-2,6-octadienyl group, etc. In a range of numbers Be-option.

In the above formula (1), the haloalkenyl group having a carbon number of a to b is a straight chain composed of a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. Represents an unsaturated hydrocarbon group which is in the form of a chain or a branched chain and has one or more double bonds in the molecule. At this time, when substituted with two or more halogen atoms, the halogen atoms may be the same as or different from each other. For example, 2,2-dichlorovinyl group, 2-fluoro-2-propenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3-bromo-2 -Propenyl group, 3,3-difluoro-2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3-dibromo-2-propenyl group, 2, 3,3-trifluoro-2-propenyl group, 2,3,3-trichloro-2-propenyl group, 1- (trifluoromethyl) ethenyl group, 3-chloro-2-butenyl group, 3-bromo-2- Butenyl group, 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group, 3-chloro-4,4,4-trifluoro-2-butenyl group, 3-bromo- 2-methyl- - propenyl group, etc. As a specific example, it may be selected from the range of the specified number of carbon atoms.

In the above formula (1), the description of the cycloalkenyl group having a carbon number of a to b is a cyclic unsaturated hydrocarbon having 1 to 2 carbon atoms and having one or more double bonds. Represents a group and can form a monocyclic or complex ring structure from 3 to 6-membered rings. Each ring may be optionally substituted with an alkyl group within a range of the specified number of carbon atoms, and the double bond may be in an endo- or exo- form. For example, 2-cyclopenten-1-yl group, 3-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, bicyclo [2.2.1] -5-heptene- A 2-yl group or the like is given as a specific example, and is selected within the range of each designated number of carbon atoms.

The notation of a halocycloalkenyl group having a carbon number of a to b in the above formula (1) is a cyclic structure having a carbon number of a to b, wherein a hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom And an unsaturated hydrocarbon group having one or two or more double bonds, and can form a monocyclic or complex ring structure having 3 to 6 members. Each ring may be optionally substituted with an alkyl group within a range of the specified number of carbon atoms, and the double bond may be in an endo- or exo- form. In addition, the substitution by a halogen atom may be a ring structure part, a side chain part or both of them, and when substituted by two or more halogen atoms, those halogen atoms May be the same as or different from each other. For example, a 2-chlorobicyclo [2.2.1] -5-hepten-2-yl group and the like can be mentioned as specific examples, and each group is selected within the range of the designated number of carbon atoms.

In the above formula (1), the alkynyl group having a carbon number of a to b is linear or branched having a carbon number of a to b and one or more triples in the molecule. Represents an unsaturated hydrocarbon group having a bond, such as ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 1-methyl-2- Specific examples include butynyl group, 1,1-dimethyl-2-propynyl group, 2-hexynyl group and the like, and each is selected within the range of the designated number of carbon atoms.

In the above formula (1), a haloalkynyl group having a carbon number of a to b is a straight chain composed of a to b carbon atoms in which a hydrogen atom bonded to the carbon atom is arbitrarily substituted with a halogen atom. Represents an unsaturated hydrocarbon group which is in the form of a chain or a branched chain and has one or more triple bonds in the molecule. At this time, when substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other. Specific examples include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of which is selected for each specified number of carbon atoms.

In the above formula (1), the notation of an alkoxy group having carbon atoms a to b represents an alkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as methoxy group, ethoxy group, n Specific examples include -propyloxy group, i-propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, and the like. Each selected range of carbon atoms is selected.

The notation of a haloalkoxy group having carbon atoms a to b in the above formula (1) represents a haloalkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as a difluoromethoxy group, trifluoro Methoxy group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2-chloro-1,1,2-trifluoroethoxy group, 2-bromo-1,1,2-trifluoroethoxy group, pentafluoroethoxy group, 2,2-dichloro-1,1,2-trifluoroethoxy group 2,2,2-trichloro-1,1-difluoroethoxy group, 2-bromo-1,1,2,2-tetrafluoroethoxy group, 2,2,3 3-tetrafluoropropyloxy group, 1,1,2,3,3,3-hexafluoropropyloxy group, 2,2,2-trifluoro-1- (trifluoromethyl) ethoxy group, heptafluoropropyloxy group Specific examples include 2-bromo-1,1,2,3,3,3-hexafluoropropyloxy group and the like, and each is selected within the range of the designated number of carbon atoms.

In the above formula (1), the notation of (alkyl of carbon atoms a to b) carbonyl group represents an alkyl-C (O) -group having the above meaning consisting of a to b carbon atoms, for example acetyl Specific examples include a group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, etc. Selected.

In the above formula (1), the notation of (haloalkyl having a carbon number of a to b) carbonyl group represents a haloalkyl-C (O) -group having the above-mentioned meaning consisting of a to b carbon atoms. Acetyl group, chloroacetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group, 3-chloro-2 Specific examples include, 2-dimethylpropanoyl group, and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of (alkoxy having carbon atoms a to b) carbonyl group in the above formula (1) represents an alkyl-O—C (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, Specific examples include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group and the like. Selected within the specified number of carbon atoms.

In the above formula (1), the expression of (haloalkoxy having a carbon number of a to b) carbonyl group represents a haloalkyl-O—C (O) — group having the above meaning consisting of a carbon number of a to b. Specific examples include 2-chloroethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, etc. Selected within the specified number of carbon atoms.

In the above formula (1), the notation of (alkylamino having a carbon number of a to b) carbonyl group is carbamoyl substituted with an alkyl group as defined above, wherein one of the hydrogen atoms is composed of a to b carbon atoms. For example, methylcarbamoyl group, ethylcarbamoyl group, n-propylcarbamoyl group, i-propylcarbamoyl group, n-butylcarbamoyl group, i-butylcarbamoyl group, s-butylcarbamoyl group, t-butylcarbamoyl group, etc. Specific examples are given, each selected in the range of the specified number of carbon atoms.

The notation of (haloalkylamino of carbon atoms a to b) carbonyl group in the above formula (1) is a carbamoyl group substituted by a haloalkyl group as defined above, wherein one of the hydrogen atoms is composed of a carbon atom of a to b Specific examples include 2-fluoroethylcarbamoyl group, 2-chloroethylcarbamoyl group, 2,2-difluoroethylcarbamoyl group, 2,2,2-trifluoroethylcarbamoyl group, and the like. Selected in the range of the number of carbon atoms.

In the above formula (1), the notation of di (alkyl having a carbon number of ab) aminocarbonyl group is such that both hydrogen atoms may be the same or different from each other from ab. A carbamoyl group substituted by an alkyl group as defined above, for example, N, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-di- Specific examples include n-propylcarbamoyl group, N, N-di-n-butylcarbamoyl group and the like, and each is selected within the range of the designated number of carbon atoms.

The substituents R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁷ of the cinnamic acid derivative represented by the formula (1) are each independently a hydrogen atom, a halogen atom, or an alkyl having 1 to 6 carbon atoms. A substituent selected from the group consisting of a group, 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 nitro group. preferable.

In addition, the substituent R ¹ is preferably a substituent other than a hydrogen atom in the above definition from the viewpoint of orientation sensitivity, and is preferably a halogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. And more preferably a substituent selected from the group consisting of a haloalkyl group, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, and a nitro group.

Examples of the divalent aromatic group of the substituent R ² include 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; as the divalent alicyclic group for R ² , for example, 1,2-cyclopropylene group, 1,3-cyclobutylene group, 1,4-cyclohexylene The divalent heterocyclic group represented by R ² includes, for example, a 1,4-pyridylene group, a 2,5-pyridylene group, a 1,4-furylene group, and the like; a divalent condensed cyclic group represented by R ² Examples of the group include a 2,6-naphthylene group. R ² is preferably a 1,4-phenylene group.

Preferred examples of the compound represented by the above formula (1) include, for example, the following formulas (1-1) to (1-5):

(In the above formulas, R ¹ are each the same meaning as R ¹ in the formula (1).) Of can be mentioned cinnamic acid derivatives represented by each.

The cinnamic acid derivative represented by the above formula (1) can be synthesized by appropriately combining organic chemistry methods.

<Reaction of monomer having epoxy group and specific cinnamic acid derivative>
The reaction product (monomer) of the monomer having an epoxy group and the specific cinnamic acid derivative used for the preparation of the polymer as the component (A) of the present invention is the monomer having the epoxy group as described above and the specific cinnamic It can be synthesized by reacting an acid derivative, preferably in the presence of a catalyst, preferably in a suitable organic solvent.
The use ratio of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 1 with respect to 1 mol of the epoxy group contained in the monomer having an epoxy group. .3 mole, more preferably 0.1 to 1.1 mole.
As the organic catalyst that can be used here, a compound known as a so-called curing accelerator that accelerates the reaction between an organic base or an epoxy compound and an acid anhydride can be used.

Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, And tertiary organic amines such as diazabicycloundecene; 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; quaternary organic amines such as tetramethylammonium hydroxide preferable.

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-methylimidazole, 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 trimellitate, 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-triazine, 2,4-diamino-6- [2'-ethyl- '-Methylimidazolyl- (1')] ethyl-s-triazine, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl] -(1 ')] Imidazole compounds such as isocyanuric acid adducts of ethyl-s-triazine; organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide , Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra -N-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate Quaternary phosphonium salts such as salts; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; zinc octylate, tin octylate, aluminum acetylacetone complex, etc. Organic metal compounds; tetraethylammonium bromide, tetra-n-butylammonium bromide, quaternary ammonium salts such as tetraethylammonium chloride, tetra-n-butylammonium chloride; boron compounds such as boron trifluoride and triphenylborate; Metal halide compounds such as zinc and stannic chloride; high melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin; imidazole compounds, organophosphorus compounds and 4 Table of curing accelerators such as grade phosphonium salts Microcapsule-type latent curing accelerator coated with polymer; amine salt-type latent curing accelerator; high-temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt and Bronsted acid salt Can be mentioned.

Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.

The ratio of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and further preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer having an epoxy group. is there.

Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. 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 such an amount 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, more preferably 5 to 50% by mass. Is done.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

Thus, a solution containing a monomer which is a reaction product of the monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1) is obtained. This solution may be used as it is for the preparation of the polymer as the component (A), may be used for the preparation of the polymer as the component (A) after isolating the monomer contained in the solution. The separated monomer may be purified and then used for the preparation of the polymer as component (A).

<Polymer of component (A)>
The polymer which is the component (A) used in the present invention is a polymer obtained by polymerizing a monomer which is a reaction product of the monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1). . The polymer of the component (A) is a copolymer of a monomer that is a reaction product of the monomer having an epoxy group and a cinnamic acid derivative represented by the above formula (1) and another polymerizable unsaturated compound. Can be.

Other polymerizable unsaturated compounds include (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclounsaturated compounds, maleimide Examples include compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds.

Specific examples thereof include methacrylic acid alkyl esters such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2- Methacryloxyethylglycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate Etc .; alkyl acrylate esters such as methyl acrylate Over DOO, isopropyl acrylate and the like; as methacrylic acid cyclic alkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decan-8-yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate and the like; acrylic acid cyclic alkyl ester such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1] .0 ^2,6] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl oxy ethyl acrylate, isobornyl acrylate, Kore stannyl acrylate; meta As aryl acrylate, phenyl methacrylate, benzyl methacrylate and the like; As acrylate aryl ester, for example, phenyl acrylate, benzyl acrylate, etc .; As unsaturated dicarboxylic acid diester, for example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .;

Examples of bicyclo unsaturated compounds include 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 and the like; as maleimide compounds, for example, phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide, etc .; unsaturated aromatic compounds such as styrene, α-methylstyrene, m- Methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc .; conjugated diene compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc. As unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .; as unsaturated dicarboxylic acid anhydride, each unsaturated dicarboxylic acid anhydride; as polymerizable unsaturated compound other than the above Examples thereof include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like.

The copolymerization ratio of the monomer which is a reaction product of the monomer having an epoxy group and the cinnamic acid derivative represented by the above formula (1) in the polymer as the component (A) is preferably 30 mol% or more. More preferably, it is 50 mol% or more. From the viewpoint of orientation sensitivity, it is more preferably 70 mol% or more.

The synthesis of the polymer as component (A) can be carried out by a known radical polymerization method, preferably in a solvent and in the presence of a suitable polymerization initiator.

Thus, a solution containing the polymer as the component (A) is obtained. This solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polymer contained in the solution, or after the isolated polymer is purified. You may use for preparation of a liquid crystal aligning agent.

<(B) component>
Component (B) in the cured film forming composition of the present invention is a crosslinking agent.
As the crosslinking agent as component (B), a compound having at least two groups capable of forming a crosslink with the thermally crosslinkable functional group of component (A) is preferable. For example, a crosslinking having at least two methylol groups or alkoxymethyl groups. It is preferable that it is an agent. Examples of the compound having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. Commercially available compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.), methylated urea resins (Trade name: UFR (registered trademark) 65), butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation (formerly Dainippon Ink Chemical Co., Ltd.) Urea / formaldehyde resin (high condensation type, trade name: Beccamin (registered trademark) J-300S, P-955, N) manufactured by Kogyo Co., Ltd.).

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

Specific examples of alkoxymethylated melamine include, for example, hexamethoxymethylmelamine. As commercially available products, methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.), butoxymethyl type melamine Compound (trade name: My Coat (registered trademark) 506, 508), methoxymethyl type melamine compound (trade name: Nicalac (registered trademark) MW-30, MW-22, MW-) manufactured by Sanwa Chemical Co., Ltd. 11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nicalac (registered trademark) MX-45, MX-410) , MX-302).

Further, as a crosslinking agent, a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group may be used. For example, the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 and the like. Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 (Nippon Cytec Industries, Ltd.). ) (Formerly Mitsui Cytec Co., Ltd.).

Further, as a crosslinking agent for the component (B), hydroxymethyl groups (that is, methylol groups) or alkoxymethyl groups such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. Polymers produced using an acrylamide compound or a methacrylamide compound substituted with a can also be used.

Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. And a copolymer of methacrylamide and benzyl methacrylate, a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.

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

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

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

Here, the specific functional group possessed by the acrylic polymer is a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types selected from these functional groups. Say functional group.

In the above-described reaction, the preferred combination of the specific functional group possessed by the acrylic polymer and the functional group possessed by the specific compound and involved in the reaction is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, or a phenolic hydroxy group. Groups and epoxy groups, carboxyl groups and isocyanate groups, amino groups and isocyanate groups, or hydroxy groups and acid chloride groups. Furthermore, a more preferable combination is an epoxy group in a carboxy group and glycidyl methacrylate, or an isocyanate group in a hydroxy group and isocyanate ethyl methacrylate.

The weight average molecular weight (polystyrene equivalent value) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000. More preferably, it is 3,000 to 50,000.

These cross-linking agents can be used alone or in combination of two or more.

The content of the crosslinking agent as the component (B) in the cured film forming composition of the present invention is preferably 1 part by mass to 500 parts by mass, more preferably based on 100 parts by mass of the polymer as the component (A). 5 parts by mass to 400 parts by mass. When content of a crosslinking agent is too small, the solvent tolerance of the cured film obtained from a cured film formation composition will fall, and liquid crystal orientation will fall. On the other hand, when the content is excessive, the liquid crystal orientation and storage stability may be lowered.

<(C) component>
The cured film forming composition of the present invention may contain 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 as the component (C). good.

Examples of the polymer as the component (C) include acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples include allylamines, celluloses (cellulose or derivatives thereof), polymers having a linear or branched structure such as phenol novolac resins and melamine formaldehyde resins, and cyclic polymers such as cyclodextrins.

The polymer as the component (C) preferably includes acrylic polymers, hydroxyalkylcyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

The acrylic polymer which is a preferred example of the polymer of component (C) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, vinyl compound, etc. It may be a polymer obtained by polymerizing a monomer containing a monomer having a functional group or a mixture thereof, and is not particularly limited with respect to the skeleton of the main chain of the polymer constituting the acrylic polymer and the type of side chain.

The monomer having a specific functional group includes a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxy group, a monomer having a carboxyl group, and an amino group. A monomer, a monomer having an alkoxysilyl group, and the following formula (2):

(Wherein R ⁶² represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a phenyl group), and a monomer having a group represented by the formula:

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

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

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

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

Examples of the monomer having an amino group described above include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

Examples of the monomer having an alkoxysilyl group include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyl, and the like. Examples include trimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.

In the above formula (2), the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms in R ⁶² are groups having the corresponding number of carbon atoms among the alkyl groups and alkoxy groups exemplified above. Is mentioned.
Examples of the monomer having a group represented by the above formula (2) include monomers having groups represented by the following formulas [2-1] to [2-5].

Moreover, in this embodiment, when synthesizing an acrylic polymer which is an example of the component (C), a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group are used as long as the effects of the present invention are not impaired. Monomers that do not have any of the groups represented can be used in combination.

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

Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, Preliminary 8-ethyl-8-tricyclodecyl acrylate.

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

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

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

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

(C) The usage-amount of the monomer which has a specific functional group used in order to obtain the acrylic polymer which is an example of a component is based on the total amount of all the monomers used in order to obtain the acrylic polymer which is (C) component, It is preferable that it is 2 mol% or more. If the monomer having a specific functional group is too small, the solvent resistance of the resulting cured film tends to be insufficient.

(C) Although the method to obtain the acrylic polymer which is an example of a component is not specifically limited, For example, the monomer containing the monomer which has a specific functional group, the monomer which does not have a specific functional group depending on necessity, a polymerization initiator, etc. Can be obtained by a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent coexisting with. In that case, the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which does not have the specific functional group used depending on necessity, a polymerization initiator, etc. Specific examples are described in the section of [Solvent] described later.

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

In addition, the acrylic polymer solution, which is an example of the component (C) obtained by the above method, is poured into diethyl ether or water under stirring to cause reprecipitation, and the generated precipitate is filtered and washed. Under normal or reduced pressure, it can be dried at room temperature or by heating to obtain an acrylic polymer powder as an example of the component (C). By the above-mentioned operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer which is an example of the component (C) can be removed, and as a result, the acrylic polymer which is an example of the purified component (C) Of powder is obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

The acrylic polymer which is a preferred example of the component (C) has a weight average molecular weight of preferably 3000 to 200000, more preferably 4000 to 150,000, and further preferably 5000 to 100,000. If the weight average molecular weight exceeds 200,000, the solvent solubility may decrease and handling may decrease. If the weight average molecular weight is less than 3,000, the curing may be insufficient during thermal curing. And solvent resistance may be reduced. The weight average molecular weight is a value obtained by using gel as a standard material by gel permeation chromatography (GPC). Hereinafter, the same applies to this specification.

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

As a polyester polyol which is a preferred example of the polymer of component (C), a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol or polypropylene glycol is reacted with a polyvalent carboxylic acid such as adipic acid, sebacic acid or isophthalic acid. Can be mentioned. Specific examples of the polyester polyol include DIC polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD- X-2555, OD-X-2560, Kuraray polyols 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 preferred example of the polymer of component (C), includes those obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of the polycaprolactone polyol include DIC polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Plaxel (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.

Examples of the polycarbonate polyol which is a preferable example of the polymer of component (C) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Specific examples of the polycarbonate polyol include Placel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Kuraray, and the like.

Examples of cellulose that is a preferred example of the polymer of component (C) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkylalkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, and cellulose. For example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

The cyclodextrin which is a preferred example of the polymer of component (C) includes cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl- methylated cyclodextrins such as γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl- β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypro Pill-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2 , 3-dihydroxypropyl-β-cyclodextrin, 2,3-dihydroxypropyl-γ-cyclodextrin, and the like.

As a preferred example of the polymer of component (C), a melamine formaldehyde resin includes a resin obtained by polycondensation of melamine and formaldehyde.

In the melamine formaldehyde resin as the component (C), it is preferable that the methylol group generated during the polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability. Examples of the melamine formaldehyde resin include a resin having a unit structure represented by the following formula.

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

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

The (C) component melamine formaldehyde resin 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 exceeds 5,000, the solubility in the solvent may decrease and handling may decrease. If the weight average molecular weight is less than 250, the curing may be insufficient during thermal curing. In some cases, the effect of improving the solvent resistance is not sufficiently exhibited.

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

Examples of the phenol novolak resin that is a preferred example of the specific polymer of the component (C) include phenol-formaldehyde polycondensate.

In the cured film forming composition of the present embodiment, the polymer of component (C) may be used in the form of a powder or in the form of a solution obtained by re-dissolving the purified powder in a solvent described later.

In the cured film forming composition of the present embodiment, the component (C) may be a mixture of a plurality of types of polymers exemplified as the component (C).

The content of the component (C) in the cured film forming composition of the present invention is preferably 400 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B). More preferably, it is 10 to 380 parts by mass, and still more preferably 40 to 360 parts by mass. When the content of the component (C) is excessive, the liquid crystal orientation tends to be lowered.

<(D) component>
The cured film forming composition of the present invention can further contain a crosslinking catalyst as the component (D) in addition to the components (A) and (B).
As the crosslinking catalyst as component (D), for example, an acid or a thermal acid generator can be preferably used. This component (D) is effective in promoting the thermosetting reaction of the cured film forming composition of the present invention.
Specific examples of the component (D) include sulfonic acid group-containing compounds, hydrochloric acid or salts thereof as the 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, camphor Sulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, sulfonic acid group-containing compounds such as dodecylbenzenesulfonic acid, Its hydrates and Etc. The.

Examples of the compound that generates an acid by heat include, for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3 -Phenylenetris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p- Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydro Shibuchiru p- toluenesulfonate, N- ethyl -p- toluenesulfonamide, further represented by the following compound:

Etc.

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

<(E) component>
This invention can also contain the component (henceforth an adhesion improvement component) which improves the adhesiveness of the cured film formed as (E) component.

(E) When using the cured film formed from the cured film forming composition of this embodiment containing a component as an alignment material, the polymerizable liquid crystal of the polymerizable liquid crystal is improved so that the adhesion between the alignment material and the polymerizable liquid crystal layer is improved. The polymerizable functional group and the crosslinking reaction site of the alignment material can be linked by a covalent bond. As a result, the retardation material of this embodiment formed by laminating a cured polymerizable liquid crystal on the alignment material of this embodiment can maintain strong adhesion even under conditions of high temperature and high humidity , such as peeling. High durability can be exhibited.

The component (E) reacts with one or more polymerizable groups and 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 the group A. Compounds having at least one group can be used.
As the component (E), monomers and polymers having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group are preferred.
Such (E) component includes a compound having a hydroxy group and a (meth) acryl group, a compound having an N-alkoxymethyl group and a (meth) acryl group, an N-alkoxymethyl group and a (meth) acryl group. The polymer etc. which have are mentioned. Specific examples are shown below.

(E) As an example of a component, the polyfunctional acrylate containing a hydroxyl group (henceforth a hydroxy group containing polyfunctional acrylate) can be mentioned.
Examples of the hydroxy group-containing polyfunctional acrylate that is an example of the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

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

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

The compound of component (E) includes a compound having at least one polymerizable group containing a C═C double bond and at least one N-alkoxymethyl group in one molecule.

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

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

As the component (E), any compound having the above-described group may be used, and a compound represented by the following formula (X1) is preferable.

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

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and 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 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 group -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 And til-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like. .

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

Another embodiment of the compound having a polymerizable group containing a C═C double bond and an N-alkoxymethyl group as component (E) is preferably a compound represented by the following formula (X2), for example. .

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 cyclic group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, An ether bond may be included in the structure.
R ⁵³ is a divalent group containing a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. And an ether bond may be included in the structure.
R ⁵⁴ is a linear or branched divalent to 9-valent aliphatic group having 1 to 20 carbon atoms, a divalent to 9-valent aliphatic cyclic group having 5 to 6 carbon atoms, or a carbon number of 5 It represents a divalent to a 9-valent aliphatic group containing 6 to 6 aliphatic rings, and one methylene group or a plurality of non-adjacent methylene groups in these groups may be replaced with an ether bond.
Z is> NCOO-, or -OCON <(where "-" indicates that there is one bond, and ">" and "<" indicate that there are two bonds, and It represents an alkoxymethyl group (that is, —OR ⁵² group) is bonded to any one of the bonds.)
r is a natural number of 2 or more and 9 or less.

Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of R ⁵³ include a divalent group obtained by further removing one hydrogen atom from an alkyl group having 2 to 20 carbon atoms.
Further, specific examples of the divalent to 9-valent aliphatic group having 1 to 20 carbon atoms in the definition of R ⁵⁴ include further removing 1 to 8 hydrogen atoms from the alkyl group having 1 to 20 carbon atoms. Examples thereof include divalent to 9-valent groups.

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 an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. Group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1, 1,2-trimethyl-n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group N-pentadecyl group, n-hexadecyl group, A heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, a cyclopentyl group, a cyclohexyl group, a group in which one or more of them are bonded in a range of up to 20 carbon atoms, and one of these groups An example is a group in which one methylene group or a plurality of methylene groups not adjacent to each other is replaced with an ether bond.

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

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

R may be a natural number of 2 to 9, but a natural number of 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 with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the crosslinking agent of the component (B). The amount is from 100 parts by weight to 100 parts by weight, and more preferably from 5 parts by weight to 70 parts by weight. (E) By making content of a component into 1 mass part or more, sufficient adhesiveness can be provided to the cured film formed. However, when the amount is more than 100 parts by mass, the liquid crystal orientation tends to decrease.

In the cured film forming composition of the present embodiment, the component (E) may be a mixture of a plurality of compounds of the component (E).

<Solvent>
The cured film forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used in that case is only required to be able to dissolve the component (A), the component (B) and, if necessary, the component (C), the component (D), the component (E) and / or other additives described below. Kinds and structures are not particularly limited.

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

When the cured film-forming composition of the present invention is used to produce an alignment material by forming a cured film on a resin film, 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 and the like are preferable from the viewpoint that the resin film is resistant. .

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

<Other additives>
Furthermore, the cured film-forming composition of the present invention is, as necessary, an adhesion improver, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stability, as long as the effects of the present invention are not impaired. Agents, antifoaming agents, antioxidants, and the like.

<Preparation of cured film forming composition>
The cured film forming composition of the present invention contains (A) component polymer and (B) component cross-linking agent, and (C) component polymer, (D) cross-linking catalyst, and (E) component adhesion as desired. It is a composition that can contain an accelerator and further other additives as long as the effects of the present invention are not impaired. Usually, they are used in the form of a solution in which they are dissolved in a solvent.

Preferred examples of the cured film forming composition of the present invention are as follows.
[1]: 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 the component (A).
[2]: Based on 100 parts by weight of component (A), component (A), 1 part by weight to 500 parts by weight of component (B), polymer (A) and crosslinking agent for component (B) A cured film forming composition containing 1 to 400 parts by mass of component (C) with respect to 100 parts by mass of the total amount of
[3]: A cured film forming composition containing 1 part by weight to 500 parts by weight of the component (B) based on 100 parts by weight of the component (A) and the component (A), and a solvent.
[4]: (A) component, based on 100 parts by mass of component (A), 1 part by mass to 500 parts by mass of component (B), polymer of component (A) and crosslinking agent of component (B) A cured film forming composition containing 1 to 400 parts by mass of component (C) and a solvent with respect to 100 parts by mass of the amount.
[5]: (A) component, based on 100 parts by mass of component (A), 1 part by mass to 500 parts by mass of component (B), the polymer as component (A) and the crosslinking agent for component (B) 1 to 400 parts by mass of component (C), 100 parts by mass of the polymer as component (A) and 100 parts by mass of the crosslinking agent of component (B) A cured film forming composition containing 20 parts by mass of component (D) and a solvent.
[6]: (A) component, based on 100 parts by mass of component (A), 1 part by mass to 500 parts by mass of component (B), (A) component polymer and (B) component cross-linking agent 1 to 400 parts by mass of component (C), 100 parts by mass of the polymer as component (A) and 100 parts by mass of the crosslinking agent of component (B) 20 parts by mass of component (D), 1 part by mass to 100 parts by mass of component (E) with respect to 100 parts by mass of the total amount of the polymer as component (A) and the crosslinking agent of component (B), and solvent A cured film-forming composition comprising:

The blending ratio, preparation method, and the like when the cured film forming composition of the present invention is used as a solution are 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 the solvent, but is 1% by mass to 60% by mass, preferably 2%. The mass is from 50% by mass to 50% by mass, and more preferably from 2% by mass to 20% by mass. Here, solid content means what remove | excluded the solvent from all the components 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, a component (B), a component (C), a component (D), a component (E), and the like are mixed in a predetermined ratio in a solution of the component (A) dissolved in a solvent, and uniform. Examples thereof include a solution method, and a method in which other additives are further added and mixed as necessary at an appropriate stage of the preparation method.

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

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

<Hardened film, alignment material and retardation material>
A solution of the cured film forming composition of the present invention is applied to a substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or ITO. Substrates) and film substrates (eg, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene) On a resin film such as a film, etc., a bar coating, spin coating, flow coating, roll coating, slit coating, spin coating following slits, ink jet coating, printing, etc. to form a coating film, Relieved Dried by heating with a plate or an oven or the like, it is possible to form a cured film. The cured film can be used as an alignment material as it is.

The heating and drying conditions may be such that the crosslinking reaction with the crosslinking agent proceeds to such an extent that the components of the cured film (alignment material) do not elute into the polymerizable liquid crystal solution applied thereon. A heating temperature and a heating time appropriately selected from the range of 200 ° C. and a time of 0.4 minutes to 60 minutes are adopted. The heating temperature and the heating time are preferably 70 to 160 ° C. and 0.5 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 is appropriately determined in consideration of the level difference of the substrate to be used and optical and electrical properties. You can choose.

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

In addition, after using the two substrates having the alignment material of the present invention formed as described above, the alignment materials on both substrates are bonded to each other via a spacer, and then between the substrates. A liquid crystal display element in which liquid crystal is injected to align the liquid crystal may be used.
Thus, the cured film forming composition of this invention can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not construed as being limited thereto.
[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Raw material>
GMA: glycidyl methacrylate M100: 3,4-epoxycyclohexylmethyl methacrylate 4MCA: 4-methoxycinnamic acid HEMA: 2-hydroxyethyl methacrylate MMA: methyl methacrylate AIBN: α, α'-azobisisobutyronitrile BMAA: N- Butoxymethylacrylamide CIN1

CIN2 (mixture of the following isomers)

CIN3

CIN4

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

<D component>
PTSA: p-toluenesulfonic acid monohydrate <E component>
E-1: Compound having a hydroxy group and an acrylic group represented by the following structural formula

E-2: Compound having an N-alkoxymethyl group and an acrylic group represented by the following structural formula

<Solvent>
As the solvent, propylene glycol monomethyl ether (PM), cyclohexanone (CH), cyclopentanone (CP), and methyl isobutyl ketone (MIBK) were used.

<Measurement of molecular weight of polymer>
The molecular weight of the acrylic copolymer in the polymerization example was as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co. And measured.
The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Standard sample for preparing calibration curve: Standard polystyrene (Molecular weight: about 197,000, 55,100, 12,800, 3,950, 1,260, 580).

Reference Example 1 Synthesis of CIN1 GMA 8.3 g (58.4 mmol), 4-methoxycinnamic acid 20.7 g (116.2 mmol), dibutylhydroxytoluene 0.2 g, triphenylethylphosphonium bromide 0.3 g, dioxane 80 mL And heated at 90 ° C. for 3 days. After completion of the reaction, dioxane was distilled off under reduced pressure, 150 mL of ethyl acetate was added and insoluble matter was filtered off, and 100 mL of sodium bicarbonate water was added and washed three times to remove excess methoxycinnamic acid. Ethyl acetate was distilled off under reduced pressure to obtain 16.5 g of the desired product, CIN1 (yield: 88%).

Reference Example 2 Synthesis of CIN2 M100 4.9 g (25.0 mmol), 4-methoxycinnamic acid 8.9 (50.0 mmol), dibutylhydroxytoluene 0.1 g, triphenylethylphosphonium bromide 0.18 g, dioxane 40 mL Was heated at 90 ° C. for 3 days. After completion of the reaction, dioxane was distilled off under reduced pressure, 100 mL of ethyl acetate was added, insoluble matter was filtered off, and 100 mL of sodium bicarbonate water was added, followed by washing three times. Ethyl acetate was distilled off under reduced pressure to obtain 6.3 g of the desired product. (Yield: 74%).

Reference Example 3 Synthesis of CIN3 CIN3 was synthesized according to the synthesis method described in JP-T-2013-514449.

Reference Example 4 Synthesis of CIN4 CIN4 was synthesized according to the synthesis method described in Polymer International 43 (1997) 317.

<Synthesis of component A>
<Polymerization example 1>
CIN1 15.0 g, HEMA 1.5 g, and AIBN 0.5 g as a polymerization catalyst were dissolved in PM 122.4 g and CH 30.6, and reacted for 20 hours under heating to reflux to produce an acrylic copolymer (PA-1 ) Was obtained. Mn of the obtained acrylic copolymer was 12,000 and Mw was 32,000.

<Polymerization example 2>
CIN1 15.0 g, AIBN 0.4 g as a polymerization catalyst was dissolved in PM 110.4 g, CH 27.6, and reacted for 20 hours under reflux with heating, whereby 10% by mass of acrylic copolymer (PA-2) was obtained. A solution containing was obtained. Mn of the obtained acrylic copolymer was 8,100 and Mw was 23,000.

<Polymerization Example 3>
CIN2 15.0 g, HEMA 1.3 g, and AIBN 0.4 g as a polymerization catalyst were dissolved in PM 120.0 g and CH 30.0, and reacted for 20 hours under heating to reflux to produce an acrylic copolymer (PA-3 ) Was obtained. Mn of the obtained acrylic copolymer was 12,000 and Mw was 41,000.

<Polymerization example 4>
CIN1 15.0 g, MMA 1.5 g, and AIBN 0.5 g as a polymerization catalyst were dissolved in PM 122.4 g and CH 30.6, and reacted for 20 hours under heating to reflux to produce an acrylic copolymer (PA-4 ) Was obtained. Mn of the obtained acrylic copolymer was 11,000 and Mw was 38,000.

<Polymerization example 5>
An acrylic copolymer (PA-5) was prepared by dissolving 15.0 g of CIN3, 1.4 g of HEMA, and 0.4 g of AIBN as a polymerization catalyst in 121.6 g of PM and CH 30.4 and reacting them under heating under reflux for 20 hours. ) Was obtained. Mn of the obtained acrylic copolymer was 9,000 and Mw was 22,000.

<Polymerization Example 6>
CIN4 15.0 g, HEMA 1.7 g, and AIBN 0.5 g as a polymerization catalyst were dissolved in 124.0 g of PM and CH 31.0, and reacted for 20 hours under reflux with heating to prepare an acrylic copolymer (PA-6). ) Was obtained. Mn of the obtained acrylic copolymer was 10,000 and Mw was 33,000.

<Polymerization example 9>
CIN1 10.0 g, HEMA 2.7 g, and AIBN 0.4 g as a polymerization catalyst were dissolved in 118.2 g of PM, and reacted for 20 hours under reflux with heating to give 10% by mass of an acrylic copolymer (PA-7). A solution containing was obtained. Mn of the obtained acrylic copolymer was 22,000 and Mw was 41,000.

<Synthesis of B component>
<Polymerization Example 7>
BMAA 100.0 g and AIBN 4.2 g as a polymerization catalyst were dissolved in PM 193.5 g 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 gradually added dropwise to 2000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain a polymer (PB-1).

<Synthesis of component C>
<Polymerization Example 8>
30.0 g of MMA, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 146.0 g of PM and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PC-1). Mn of the obtained acrylic copolymer was 18,000 and Mw was 32,800.

<Preparation of polymerizable liquid crystal solution>
<Preparation Example 1>
Polymeric liquid crystal LC242 (manufactured by BASF) 29.0g, Irgacure 907 (manufactured by BASF) 0.9g as a polymerization initiator, BYK-361N (manufactured by BYK) 0.2g as a leveling agent, and MIBK as a solvent were added. A polymerizable liquid crystal solution (RM-1) having a solid content concentration of 30% by mass was obtained.

<Preparation Example 2>
29.0 g of polymerizable liquid crystal LC242 (manufactured by BASF), 0.9 g of Irgacure 907 (manufactured by BASF) as a polymerization initiator, 0.2 g of BYK-361N (manufactured by BYK) as a leveling agent, and CP as a solvent were added. A polymerizable liquid crystal solution (RM-2) having a solid content concentration of 30% by mass was obtained.

<Example 1>
(A) an amount corresponding to 100 parts by mass in terms of an acrylic copolymer (PA-1) in a solution containing 10% by mass of the acrylic copolymer (PA-1) obtained in Polymerization Example 1 as a component, (B) 30 parts by mass of HMM as the component, 3 parts by mass of PTSA as the (D) component, PM and CH are added thereto, the solvent composition is PM: CH = 80: 20 (mass ratio), and the solid content concentration is A 5.0 mass% alignment material-forming composition (A-1) was prepared.

<Examples 2 to 9 and Comparative Examples 1 to 3>
Alignment material forming compositions A-2 to A-12 were respectively prepared in the same manner as in Example 1 except that the types and amounts of the respective components were as shown in Table 1.

<Examples 10 to 18 and Comparative Examples 4 to 6>
[Evaluation of orientation]
The alignment agent compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were applied on a TAC film at a wet film thickness of 4 μm using a bar coater. Each was heated and dried in a heat circulation oven at a temperature of 110 ° C. for 60 seconds to form a cured film on the TAC film. Each cured film was irradiated vertically with 313 nm linearly polarized light at an exposure amount of 20 mJ / cm ² to form an alignment material. On the alignment material on the TAC film, a polymerizable liquid crystal solution (RM-1) or (RM-2) was applied with a wet film thickness of 6 μm using a bar coater. This coating film was dried on a hot plate at a temperature of 90 ° C. for 60 seconds and then exposed at 300 mJ / cm ² to produce a retardation material. The phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of the phase difference characteristic in the phase difference material is observed, ○ if the phase difference is expressed without defects, and no phase difference is expressed The thing was described as "x" in the column of "orientation". The evaluation results are summarized in Table 2 later.

As shown in Table 2, in Examples 10 to 18, the obtained retardation material showed good alignment even when any of the polymerizable liquid crystal solutions RM-1 and RM-2 was used.

On the other hand, in Comparative Examples 4 to 5, the retardation material obtained using RM-1 showed good orientation, but the retardation material obtained using RM-2 had good orientation. It was not obtained.

Further, in Comparative Example 6, the phase difference material did not have good orientation even when either RM-1 or RM-2 was used.

<Example 19>
An amount corresponding to 100 parts by mass in terms of an acrylic copolymer (PA-7) in a solution containing 10% by mass of the acrylic copolymer (PA-7) obtained in Polymerization Example 9 as the component (A), (B) 30 parts by mass of HMM as the component, 3 parts by mass of PTSA as the (D) component, PM and CH are added thereto, the solvent composition is PM: CH = 80: 20 (mass ratio), and the solid content concentration is A 5.0% by mass alignment material-forming composition (A-13) was prepared.

<Examples 20 to 22>
[Evaluation of orientation]
The alignment agent compositions of Examples 1 to 2 and 19 were applied on a TAC film at a wet film thickness of 4 μm using a bar coater. Each was heated and dried in a thermal circulation oven at a temperature of 90 ° C. for 60 seconds to form a cured film on the TAC film. The linearly polarized light of 313nm in the cured film was irradiated perpendicularly with an exposure amount of 5 mJ / cm ² or 20 mJ / cm ^2, to form an alignment material. On the alignment material on the TAC film, a polymerizable liquid crystal solution (RM-1) was applied with a wet film thickness of 6 μm using a bar coater. 60 seconds after drying this coating temperature 90 ° C. on a hot plate, exposed with 300 mJ / cm ^2, to produce a phase difference member. The phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of the phase difference characteristic in the phase difference material is observed, ○ if the phase difference is expressed without defects, and no phase difference is expressed The thing was described as "x" in the column of "orientation". The evaluation results are summarized in Table 3 later.

The cured film forming composition according to the present invention is very useful as a material for forming a liquid crystal alignment film of a liquid crystal display element and an alignment material for forming an optically anisotropic film provided inside or outside the liquid crystal display element. In particular, it is suitable as a material for a phase difference material of a circularly polarizing plate used as an antireflection film for an IPS-LCD or an organic EL display.

Claims (12)

1. (A) a polymer obtained by using a monomer which is a reaction product of a monomer having an epoxy group and a cinnamic acid derivative represented by the following formula (1), and (B) a cured film forming composition containing a crosslinking agent object.
   

   

   (In Formula (1), A ¹ and A ² each independently represent a hydrogen atom or a methyl group, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Haloalkyl group, cycloalkyl group having 3 to 8 carbon atoms, halocycloalkyl group having 3 to 8 carbon atoms, alkenyl group having 2 to 6 carbon atoms, haloalkenyl group having 2 to 6 carbon atoms, carbon atom A cycloalkenyl group having 3 to 8 carbon atoms, a halocycloalkenyl group having 3 to 8 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a haloalkynyl group having 2 to 6 carbon atoms, and an alkoxy having 1 to 6 carbon atoms Group, haloalkoxy group having 1 to 6 carbon atoms, (alkyl having 1 to 6 carbon atoms) carbonyl group, (haloalkyl having 1 to 6 carbon atoms) carbonyl group, (alkoxy having 1 to 6 carbon atoms) carbonyl Group, Haloalkoxy having 1 to 6 carbon atoms) carbonyl group, (alkylamino having 1 to 6 carbon atoms) carbonyl group, (haloalkyl having 1 to 6 carbon atoms) aminocarbonyl group, di (having 1 to 6 carbon atoms) Alkyl) aminocarbonyl group, a substituent selected from the group consisting of a cyano group and a nitro group, R ² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent group. R ³ represents a single bond, an oxygen atom, —COO— or —OCO—, and R ⁴ to R ⁷ each independently represents a hydrogen atom, a halogen atom, or an alkyl having 1 to 6 carbon atoms. A substituent selected from the group consisting of a group, 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 nitro group; n is an integer from 0 to 3 )
2. (B) The cured film forming composition of Claim 1 whose crosslinking agent is a crosslinking agent which has a methylol group or an alkoxymethyl group.
3. The cured film forming composition according to claim 1 or 2, further comprising (C) 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.
4. (D) The cured film formation composition as described in any one of Claims 1 thru | or 3 which further contains a crosslinking catalyst.
5. (E) one or more polymerizable groups and 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 that reacts with the group A The cured film forming composition as described in any one of Claims 1 thru | or 4 containing the compound which has these.
6. The cured film forming composition according to any one of claims 1 to 4, comprising 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A).
7. The component (C) according to any one of claims 3 to 6, comprising 1 part by mass to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B). Cured film forming composition.
8. The component (D) according to any one of claims 4 to 7, comprising 0.01 to 20 parts by mass of the component (D) with respect to 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B). The cured film forming composition as described.
9. The component (E) according to any one of claims 5 to 8, comprising 1 part by mass to 100 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of the crosslinking agent of the component (A) and the component (B). Cured film forming composition.
10. A cured film obtained by curing the cured film-forming composition according to claim 1.
11. An alignment material formed by curing the cured film forming composition according to any one of claims 1 to 9.
12. A phase difference material having a cured film obtained by curing the cured film forming composition according to claim 1.