KR20190127787A - Cured film formation composition, orientation material, and phase difference material - Google Patents

Abstract

(식(1) 중, A¹과 A²는 각각 독립적으로 수소원자 또는 메틸기를 나타내고, R¹은 수소원자, 할로겐원자 등을 나타내고, R²는 2가의 방향족기, 2가의 지환족기, 2가의 복소환식기 또는 2가의 축합환식기를 나타내고, R³은 단결합, 산소원자 등을 나타내고, R⁴~R⁷은 각각 독립적으로 수소원자, 할로겐원자 등을 나타내고, n은 0~3의 정수이다.)[PROBLEMS] To provide a cured film-forming composition which is used as an alignment material and forms a cured film exhibiting excellent liquid crystal orientation and light transmittance when a layer of polymerizable liquid crystal is disposed thereon.
[Solution] A cured film-forming composition containing (A) a reaction product of an epoxy group, a cinnamic acid derivative represented by the following formula (1), and (B) a crosslinking agent, and is formed using the composition. It has a cured film obtained using an orientation material and the said composition, The phase difference material characterized by the above-mentioned.

(In formula (1), A <^1> and A <^2> respectively independently represent a hydrogen atom or a methyl group, R <^1> represents a hydrogen atom, a halogen atom, etc., R <^2> is a bivalent aromatic group, a bivalent alicyclic group, bivalent Heterocyclic group or a bivalent condensed cyclic group is represented, R <^3> represents a single bond, an oxygen atom, etc., R <^4> -R <^7> respectively independently represents a hydrogen atom, a halogen atom, etc., n is an integer of 0-3. .)

Description

Cured film formation composition, orientation material, and phase difference material

The present invention relates to a cured film-forming composition, an alignment material and a phase difference material which can be used as a liquid crystal alignment agent for photoalignment for orienting liquid crystal molecules. In particular, the present invention can be used as a liquid crystal aligning agent for optical alignment, which is useful for producing a patterned phase difference material used in circular polarized glasses type 3D display, or a phase difference material used in circular polarizing plate used as an anti-reflection film of an organic EL display. It relates to a cured film formation composition, an orientation material, and a phase difference material.

In the case of a 3D display of circularly polarized glasses, a phase difference material is usually disposed on a display element for forming an image such as a liquid crystal panel. In this retardation material, two or more types of retardation areas having different retardation characteristics are arranged regularly and constitute a patterned retardation material. In addition, in this specification, the phase difference material patterned so that this phase difference characteristic may arrange several phase difference area | regions is called a patterned phase difference material hereafter.

As disclosed in Patent Literature 1, the patterned retardation material can be produced by optical patterning a retardation material made of a polymerizable liquid crystal. Optical patterning of the retardation material consisting of a polymerizable liquid crystal utilizes a photoalignment technique known for forming alignment of liquid crystal panels. That is, the coating film which consists of a photo-alignment material is provided on a board | substrate, and two types of polarization in which a polarization direction differs are irradiated to this. Then, an optical alignment film is obtained as an alignment material in which two kinds of liquid crystal alignment regions in which the alignment control directions of the liquid crystals are different are formed. The solution phase retardation material containing a polymeric liquid crystal is apply | coated on this photo-alignment film, and the orientation of a polymeric liquid crystal is implement | achieved. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

The antireflection film of the organic EL display is composed of a linear polarizing plate and a quarter-wave retardation plate, and converts the extraneous light directed toward the panel surface of the image display panel into linearly polarized light by the linear polarizing plate, followed by a quarter-wave retardation plate. To circularly polarized light. The extraneous light due to the circularly polarized light is reflected on the surface of the image display panel and the like, but the rotation direction of the polarization plane is reversed at this time of reflection. As a result, the reflected light is converted into linearly polarized light in the direction of shielding by the linearly polarizing plate from the quarter-wave retardation plate, and then is shielded by the subsequent linear polarizing plate, as opposed to the arrival. Emissions are significantly suppressed.

Regarding this quarter-wave retardation plate, Patent Literature 2 configures the quarter-wave retardation plate by combining a half-wave plate and a quarter-wave plate to configure this optical film by reverse dispersion characteristics. Is proposed. In the case of this method, in the wide wavelength band provided for the display of a color image, the optical film can be comprised by the reverse dispersion characteristic using the liquid crystal material by a positive dispersion characteristic.

In recent years, as a liquid crystal material applicable to this phase difference layer, what has reverse dispersion characteristic is proposed (patent document 3, 4). According to the liquid crystal material having such reverse dispersion characteristics, instead of forming a quarter-wave retardation plate using two phase retardation layers by combining a half-wave plate and a quarter-wave plate, the retardation layer is composed of a single layer. Therefore, the reverse dispersion characteristic can be secured, and thus, an optical film capable of securing a desired phase difference in a wide wavelength band can be realized by a simple configuration.

In order to orientate a liquid crystal, an alignment layer is used. As a method of forming the alignment layer, for example, a rubbing method and a photoalignment method are known, and the photoalignment method is useful in that static electricity and dust, which are problems of the rubbing method, are not generated and quantitative alignment control can be controlled. .

In the orientation reforming using the photo-alignment method, an acrylic resin, a polyimide resin, or the like having photodimerization sites such as cinnamoyl group and chalcone group in side chains is known as a usable photo-alignment material. It is reported that these resins show the performance (henceforth liquid crystal orientation) which controls the orientation of a liquid crystal by irradiating polarized UV (refer patent document 5-patent document 7.).

In addition to the liquid crystal alignment ability, solvent resistance is required for the alignment layer. For example, the alignment layer may be exposed to heat or a solvent in the manufacturing process of the phase difference material. When the alignment layer is exposed to the solvent, there is a fear that the liquid crystal alignment ability is significantly lowered.

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

Japanese Patent Publication No. 2005-49865 Japanese Patent Application Laid-Open No. H10-68816 United States Patent No. 8119026 Japanese Patent Publication No. 2009-179563 Japanese Patent No. 361342 Japanese Patent Publication No. 2009-058584 Japanese Patent Publication No. 2001-517719 Japanese Patent No. 4207430

As described above, the phase difference material is formed by stacking a cured polymerizable liquid crystal layer on the photoalignment film that is the alignment material. For this reason, the development of the orientation material which can satisfy the outstanding liquid crystal orientation and solvent resistance is calculated | required.

However, according to the examination of the present inventors, it was found that the acrylic resin having a photodimerization site such as cinnamoyl group or chalcone group in the side chain does not obtain sufficient properties when applied to the formation of the phase difference material. In particular, in order to form an orientation material by irradiating polarized UV to these resin, and to produce the phase difference material which consists of a polymeric liquid crystal using this orientation material, a large amount of polarization UV exposure is needed. The amount of polarized UV exposure is significantly greater than the amount of polarized UV exposure (for example, about 30 mJ / cm ² ) sufficient to orient the liquid crystal for a normal liquid crystal panel.

The reason why the amount of polarized UV exposure increases is that in the case of retardation formation, unlike the liquid crystal for liquid crystal panel, a polymerizable liquid crystal is used in the state of a solution, and is applied on the alignment material.

In the case where an alignment material is formed using an acrylic resin having a light dimerization site such as cinnamoyl group in the side chain, and the polymerizable liquid crystal is to be oriented, in the acrylic resin or the like, optical crosslinking by photodimerization reaction is performed. Do it. And it is necessary to perform polarization irradiation of a large exposure amount until the tolerance with respect to a polymeric liquid crystal solution is expressed. In order to orientate the liquid crystal of the liquid crystal panel, usually, only the surface of the photo-alignment alignment material may be dimerized. However, if the solvent resistance is to be expressed in the alignment material using conventional materials such as the acrylic resin described above, it is necessary to cause the reaction to the inside of the alignment material, and more exposure amount is required. As a result, there existed a problem that the orientation sensitivity of the conventional material becomes very small.

Moreover, in order to express such solvent tolerance to resin which is the conventional material mentioned above, the technique of adding a crosslinking agent is known. However, after performing a thermosetting reaction with a crosslinking agent, a problem arises in that a three-dimensional structure is formed inside the formed coating film and the photoreactivity is lowered. That is, the orientation sensitivity greatly decreased, and even if the crosslinking agent was added to the conventional material and used, the desired effect was not obtained.

From the above, there is a demand for a photoalignment technique capable of improving the alignment sensitivity of an alignment material and reducing the amount of polarized UV exposure, and a cured film forming composition that can be used as a liquid crystal alignment agent for photoalignment used to form the alignment material. There is a demand for a technology capable of providing a phase difference material with high efficiency.

The objective of this invention is made | formed based on the above knowledge and examination result. That is, the objective of this invention is providing the cured film formation composition which has the outstanding solvent resistance and can be used as a liquid crystal aligning agent for photo-alignments for providing the orientation material which can orientate a polymeric liquid crystal with high sensitivity.

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

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors selected the cured film formation material based on the reaction product of (A) the polymer which has an epoxy group, a specific cinnamic acid derivative, and (B) crosslinking agent, and was excellent content. It discovered that it was able to form the cured film (orientation material) which can have orientation, and can align a polymeric liquid crystal with high sensitivity, and completed this invention.

That is, the present invention is a first aspect,

(A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative represented by the following formula (1), and

[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, a haloalkyl group having 1 to 6 carbon atoms, A cycloalkyl group having 3 to 8 carbon atoms, a halocycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, and a carbon atom Halocycloalkenyl groups having 3 to 8 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, haloalkynyl groups having 2 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, haloalkoxy groups having 1 to 6 carbon atoms, and (carbon atoms) 1-6 alkyl) 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 and (1 to 6 carbon atoms) Alkylamino) carbonyl group, (haloalkyl having 1 to 6 carbon atoms) aminocarbonyl group, di (with 1 to 6 carbon atoms) An alkyl) aminocarbonyl group, a cyano group and a substituent selected from the group consisting of nitro groups, R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, and R ³ is a A bond, an oxygen atom, -COO- or -OCO-, and R ⁴ to R ⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and 1 carbon atom A substituent selected from the group consisting of alkoxy group of ˜6, haloalkoxy group of 1 to 6 carbon atoms, cyano group, and nitro group, and n is an integer of 0 to 3.)

(B) cross-linking system

It relates to a cured film-forming composition containing.

As a 2nd viewpoint, (B) crosslinking agent relates to the cured film formation composition as described in a 1st viewpoint which is a crosslinking agent which has a methylol group or an alkoxy methyl group.

As a 3rd viewpoint, the hardening as described in a 1st viewpoint or a 2nd viewpoint which further contains the polymer which has at least 1 group chosen from the group which consists of (C) a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. It relates to a film forming composition.

As a 4th viewpoint, it is related with the cured film formation composition in any one of a 1st viewpoint thru | or a 3rd viewpoint which further contains (D) crosslinking catalyst.

As a fifth aspect, (E) at least one group A selected from the group consisting of at least one polymerizable group and a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or at least one reacted with this group A It relates to the cured film formation composition in any one of a 1st viewpoint thru | or a 4th viewpoint containing the compound which has group.

As a 6th viewpoint, it is related with the cured film formation composition in any one of a 1st viewpoint thru | or a 5th viewpoint which contains 1 mass part-500 mass parts (B) component based on 100 mass parts of (A) component. .

Hardening as described in any one of a 3rd viewpoint thru | or a 6th viewpoint containing 1 mass part-400 mass parts (C) component with respect to 100 mass parts which is a total amount of (A) component and (B) component as a 7th viewpoint. It relates to a film forming composition.

Hardening as described in any one of 4th-7th viewpoint which contains 0.01 mass part-20 mass parts (D) component with respect to 100 mass parts which is a total amount of (A) component and (B) component as a 8th viewpoint. It relates to a film forming composition.

Hardening as described in any one of 5th viewpoint thru | or 8th viewpoint which contains 1 mass part-100 mass parts (E) component with respect to 100 mass parts which is a total amount of (A) component and (B) component as a 9th viewpoint. It relates to a film forming composition.

As a 10th viewpoint, it is related with the cured film obtained using the cured film formation composition in any one of a 1st viewpoint thru a 9th viewpoint.

As an 11th viewpoint, it is related with the orientation material formed using the cured film formation composition in any one of a 1st viewpoint thru a 9th viewpoint.

As a 12th viewpoint, it is related with the phase difference material which has a cured film obtained using the cured film formation composition in any one of a 1st viewpoint thru a 9th viewpoint.

According to this invention, the cured film which has the outstanding solvent resistance and can align a polymeric liquid crystal with high sensitivity, and the cured film formation composition suitable for the formation can be provided.

According to the present invention, it is possible to provide an alignment material excellent in liquid crystal alignment and light transmittance and a phase difference material capable of high-precision optical patterning.

<Cured film forming composition>

The cured film formation composition of this invention contains the reaction product of the polymer which has an epoxy group, and the specific cinnamic acid derivative, and (B) crosslinking agent. In addition to the said (A) component and (B) component, the cured film formation composition of this invention is further selected from the group which consists of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group as (C) component. It may contain a polymer having at least one group. In addition, a crosslinking catalyst may also be contained as (D) component. Further (E) at least one group A selected from the group consisting of at least one polymerizable group and a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or at least one group reacting with this group A It may contain a compound having. And other additives can be contained unless the effect of this invention is impaired.

Hereinafter, the detail of each component is demonstrated.

<(A) component>

(A) component contained in the cured film formation composition of this invention is a reaction product of the polymer which has an epoxy group, and the cinnamic-acid derivative represented by said Formula (1).

<Polymer with Epoxy Group>

The polymer having an epoxy group may be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group with another polymerizable unsaturated compound.

As a specific example of the polymerizable unsaturated compound which has an epoxy group, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl (alpha)-ethylacrylate, glycidyl (alpha) -n-propyl acrylate, alpha-n- Glycidyl butyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, (alpha)-ethylacrylic acid -6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned.

As another polymerizable unsaturated compound, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compounds, maleimide compounds, Unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and polymerizable unsaturated compounds other than these are mentioned.

As these specific examples, as methacrylic acid alkyl ester, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate , Diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 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 .; As alkyl acrylate, For example, methyl acrylate, isopropyl acrylate, etc .; As methacrylic cyclic alkyl ester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isobonyl methacrylate, cholestanyl methacrylate, and the like; As cyclic cyclic alkylester, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl acrylate, isobonyl acrylate, cholestanyl acrylate and the like; As methacrylic acid aryl ester, Phenyl methacrylate, benzyl methacrylate, etc .; As acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate, etc .; As unsaturated dicarboxylic acid diester, For example, diethyl maleate, diethyl fumarate, diethyl itaconic acid;

As the bicyclounsaturated compounds, for example, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept -2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'- Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2 .1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like; As maleimide compounds, for example, phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like; As an unsaturated aromatic compound, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc .; As a conjugated diene type compound, 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene, etc .; As unsaturated monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .; As unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .; As an unsaturated dicarboxylic acid anhydride, each anhydride of the said unsaturated dicarboxylic acid; As a polymerizable unsaturated compound of that excepting the above, an acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate etc. are mentioned, for example.

Preferably the copolymerization ratio of the polymerizable unsaturated compound which has an epoxy group in the polymer which has an epoxy group is 30 mass% or more, More preferably, it is 50 mass% or more.

Synthesis | combination of the polymer which has an epoxy group, Preferably it can carry out by the well-known radical polymerization method in presence of a suitable polymerization initiator in a solvent.

As a polymer which has an epoxy group, you may use a commercial item. As such a commercial item, for example, EHPE3150, EHPE3150CE (above, made by Daicel Co., Ltd.), UG-4010, UG-4035, UG-4040, UG-4070 (above, ARUFON series made by Dong-A Synthetic Co., Ltd.), ECN -1299 (product of Asahi Kasei Co., Ltd.), DEN431, DEN438 (above, Dow Chemical Co., Ltd.), jER-152 (product made in Japan Epoxy Resin Co., Ltd.), epiclon N-660, N-665, N-670, N -673, N-695, N-740, N-770, N-775 (above, made by Nippon Ink Chemical Co., Ltd.), EOCN-1020, EOCN-102S, EOCN-104S (above, Nippon Gunpowder Co., Ltd. )) Etc. can be mentioned.

<Cinnamon derivative having carboxyl group>

As a cinnamic acid derivative which has the said carboxyl group, the compound represented by said Formula (1) is mentioned.

As a halogen atom in said Formula (1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. In addition, the description of "halo" in this specification also shows these halogen atoms.

In the above formula (1), the description of the alkyl group having a to b carbon atoms indicates a straight or branched hydrocarbon group having a to b carbon atoms, for example, methyl, ethyl, n-propyl, or 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-ethyl Propyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl A group, a 1, 3- dimethyl butyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, etc. are mentioned as a specific example, and it selects from the range of each designated carbon atom number.

In the formula (1), the description of the haloalkyl group having a carbon atom a to b is a straight or branched hydrocarbon having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. In this case, when substituted by 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, iodine methyl group, difluoromethyl group, chlorofluoromethyl group, dichloromethyl group, bromofluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group, dichlorofluoro Methyl group, trichloromethyl group, bromodifluoromethyl group, bromochlorofluoromethyl group, dibromofluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoro Ethyl group, 2-chloro-2-fluoroethyl group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-di Fluoroethyl 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, pentafluoroethyl group, 1- Loro-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-bromo-3,3-difluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2-chloro-3,3,3-trifluoropropyl group, 2,2, 3,3,3-pentafluoropropyl 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-heptafluorobutyl 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, Specific examples include 1-dimethylethyl group, 5-chloro-2,2,3,4,4,5,5-heptafluoropentyl group, tridecafluorohexyl group, and the like. Is selected from the range of.

In the above formula (1), the description of the cycloalkyl group having a carbon number a to b represents a cyclic hydrocarbon group having a to b carbon atoms, and can form a monocyclic or complex ring structure from three to six member rings. have. In addition, each ring may be optionally substituted by an alkyl group in the range of the designated carbon atoms. For example, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclophene Methyl, 2-methylcyclopentyl, 3-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, bicyclo [2.2.1] heptane- 2-yl group etc. are mentioned as a specific example, and it selects from the range of carbon atom number of each designation.

The description of the halocycloalkyl group having a carbon atom number a to b in the formula (1) indicates a cyclic hydrocarbon group having a to b carbon atom atoms in which the hydrogen atom bonded to the carbon atom is optionally substituted with a halogen atom, Monocyclic or complex ring structures can be formed from three-membered rings to six-membered rings. In addition, each ring may be optionally substituted by an alkyl group within a specified number of carbon atoms, and the substitution by a halogen atom may be a ring structure portion, a side chain portion, or both thereof, or two or more halogens. When substituted by an atom, these 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-methylcyclopropyl 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, etc. are mentioned as a specific example, and it selects from the range of each designated carbon atom number.

In the formula (1), the description of the alkenyl group having a carbon atom a to b is a straight or branched chain having a to b carbon atoms, and an unsaturated hydrocarbon having one or two or more double bonds in the molecule. Group, for example, a 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, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 2-ethyl-2-propenyl, 1,1-dimethyl-2-propenyl, 2-hexenyl, 2- A methyl-2-pentenyl group, a 2, 4- dimethyl-2, 6-heptadienyl group, a 3, 7- dimethyl- 2, 6- octadienyl group, etc. are mentioned as a specific example, and each of the designated carbon atoms of Is selected from the range.

In the formula (1), the description of the haloalkenyl group having a carbon atom number a to b is a straight or branched chain consisting of a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. And unsaturated hydrocarbon groups having one or two or more double bonds in the molecule. At this time, when substituted by two or more halogen atoms, these 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-dibro Mother-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-2-propenyl group, etc. are mentioned as a specific example, and it selects from the range of each designated carbon atom number.

In the formula (1), the description of the cycloalkenyl group having a carbon atom a to b represents a cyclic unsaturated carbon group having a to b carbon atoms and an unsaturated hydrocarbon group having one or two or more double bonds, To 6-membered rings can be formed monocyclic or complex ring structure. In addition, each ring may be optionally substituted by the alkyl group in the range of the designated carbon atom, and further, the double bond may be in the form of endo- or exo-. 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 etc. are mentioned as a specific example, and it selects from the range of each designated carbon atom number.

The description of the halocycloalkenyl group having a carbon atom number a to b in the formula (1) indicates that the hydrogen atom bonded to the carbon atom is a cyclic, consisting of a to b carbon atoms in which a hydrogen atom is optionally substituted with a halogen atom. An unsaturated hydrocarbon group having two or two or more double bonds can be represented, and a monocyclic or complex ring structure can be formed from a three-membered ring to a six-membered ring. In addition, each ring may be optionally substituted by the alkyl group in the range of the designated carbon atom, and further, the double bond may be in the form of endo- or exo-. In addition, the substitution by a halogen atom may be a ring structure part, a side chain part, or both, and when substituted by two or more halogen atoms, these halogen atoms may be the same or mutually It may be different. For example, a 2-chlorobicyclo [2.2.1] -5-hepten-2-yl group etc. are mentioned as a specific example, and it selects from the range of the number of carbon atoms of each designation.

In the formula (1), the description of the alkynyl group having a to b carbon atoms is a straight or branched chain having a to b carbon atoms, and an unsaturated hydrocarbon having one or two or more triple bonds in the molecule. Group, for example, an ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group, 1-methyl-2-butynyl group, 1,1 A dimethyl-2-propynyl group, 2-hexynyl group, etc. are mentioned as a specific example, and it selects from the range of carbon atom number of each designation.

In the formula (1), the description of the haloalkynyl group having a carbon atom number a to b is a straight or branched chain consisting of a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. And unsaturated hydrocarbon groups having one or two or more triple bonds in the molecule. In this case, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, 2-chloroethynyl group, 2-bromoethynyl group, 2-iodineethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodine-2-propy And a specific example thereof may be cited, and selected from the range of the number of carbon atoms specified for each.

In the above formula (1), the description of the alkoxy group having a to b carbon atoms indicates an alkyl-O- group having the above meaning consisting of a to b carbon atoms, for example, a methoxy group, an ethoxy group and n- Specific examples include a 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. These are mentioned, and it selects from the range of each designated carbon atom number.

The description of the haloalkoxy group of carbon atom number a-b in said Formula (1) shows the haloalkyl-O- group of said meaning which consists of a-b carbon atom, for example, a difluoromethoxy group, Trifluoromethoxy 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, penta Fluoroethoxy 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, 2-bromo-1,1,2,3,3,3-hex And the like fluoro propyl oxy group as a specific example, it is selected in the range of carbon atoms of each of the specified.

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

In the above formula (1), the description of the (haloalkyl) carbonyl group having a carbon atom number a to b represents a haloalkyl-C (O)-group having the above meaning consisting of a to b carbon atoms, for example, Low acetyl group, chloroacetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, Heptafluorobutanoyl group, 3-chloro-2, 2- dimethyl propanoyl group, etc. are mentioned as a specific example, and it selects from the range of the number of carbon atoms of each designation.

The description of the (alkoxy) alkoxy) carbonyl group in the formula (1) represents an alkyl-OC (O)-group having the above meaning consisting of a to b carbon atoms, for example, a methoxycarbonyl group , Ethoxycarbonyl group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, etc. are mentioned as a specific example, and each of the designated carbon atom number Is selected from the range.

In the formula (1), the description of the (haloalkoxy) carbonyl group having a carbon atom number a to b represents a haloalkyl-OC (O)-group having the above meaning consisting of a to b carbon atoms, for example, 2 -Chloroethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, etc. are mentioned as a specific example, It is selected from the range of each designated carbon atom.

In the formula (1), the description of the (alkylamino) carbonyl group having a carbon atom a to b represents a carbamoyl group substituted with an alkyl group having one of the above meanings in which one of the hydrogen atoms has a to b carbon atoms. For example, methyl carbamoyl group, ethyl carbamoyl group, n-propyl carbamoyl group, i-propyl carbamoyl group, n-butyl carbamoyl group, i-butyl carbamoyl group, s-butyl carbamoyl group, t A butyl carbamoyl group etc. are mentioned as a specific example, and it selects from the range of carbon atom number of each designation.

In the above formula (1), the description of the (haloalkyl carbon atoms having a to b carbon atoms) aminocarbonyl group refers to a carbamoyl group substituted with a haloalkyl group having one of hydrogen atoms having the a to b carbon atoms mentioned above. And, for example, 2-fluoroethyl carbamoyl group, 2-chloroethyl carbamoyl group, 2,2-difluoroethyl carbamoyl group, 2,2,2-trifluoroethyl carbamoyl group, etc. It is mentioned as an example and is selected from the range of each designated carbon atom number.

The description of the di (alkyl of a to b carbon atoms) aminocarbonyl group in the formula (1) means that the hydrogen atoms each have the same a or b carbon atoms in which both may be the same or different from each other. Carbamoyl group substituted by phosphorus alkyl group, 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 are selected from the ranges of the designated carbon atoms.

Substituents R ¹ , R ⁴ , R ⁵ , R ⁶ and R ⁵ of the cinnamic acid derivative represented by formula (1) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom 1 It is preferable that it is a substituent selected from the group which consists of a haloalkyl group of -6, the alkoxy group of 1-6 carbon atoms, the haloalkoxy group of 1-6 carbon atoms, a cyano group, and a nitro group.

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, a haloalkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. More preferred are substituents selected from the group consisting of an alkoxy group, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group and a nitro group.

As a bivalent aromatic group of substituent R <^2> , it is a 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; As a bivalent alicyclic group of R <^2> , For example, a 1, 2- cyclopropyl group, a 1, 3- cyclobutylene group, a 1, 4- cyclohexylene group etc .; As a bivalent heterocyclic group of R <^2> , For example, 1, 4-pyridylene group, 2, 5- pyridylene group, 1, 4- furanylene group, etc .; As a bivalent condensed cyclic group of R <^2> , a 2, 6- naphthylene group etc. are mentioned, respectively. As R ^{2, a} 1,4-phenylene group is preferable.

As a preferable example of a compound represented by said Formula (1), it is following formula (1-1)-(1-5)

[Formula 2]

(In formula, R <^1> is synonymous with R <^1> in said Formula (1), respectively.) The cinnamic acid derivative etc. which are represented by each of these are mentioned.

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

<Reaction of Epoxy Group with Specific Cinnamic Acid Derivatives>

The reaction product of the polymer having an epoxy group and the specific cinnamic acid derivative contained in the cured film-forming composition of the present invention is a polymer having an epoxy group and the specific cinnamic acid derivative as described above, preferably in the presence of a catalyst, preferably suitable organic It can synthesize | combine by making it react in a 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 1.3 mol, still more preferably 0.1 to 1 mol of the epoxy group contained in the polymer having an epoxy group. 1.1 moles.

On the other hand, as a ratio of the epoxy group reacting with a cinnamic acid derivative, the range achieved is preferable as a result of the said use ratio, but it is especially preferable that it is 80 mol%-100 mol% of the whole epoxy group from a viewpoint of optical orientation.

As an organic catalyst which can be used here, a well-known compound can be used as what is called a hardening accelerator which accelerates reaction of an organic base or an epoxy compound, and an acid anhydride.

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

As said hardening accelerator, For example, tertiary amines, such as benzyl dimethylamine, 2,4,6- tris (dimethylaminomethyl) phenol, cyclohexyl dimethylamine, 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-methyldi Midazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl)- 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2- Cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimelli Tate, 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4- Diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s -tree Gin, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, Isocyanuric acid adduct of 2-phenylimidazole and isocyanuric acid adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine Imidazole compounds; Organophosphorus compounds such as diphenylphosphine, triphenylphosphine and triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide (ethyltriphenylphosphonium bromide), n-butyltriphenylphosphonium bromide, tetraphenylphosphate Phosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, Quaternary phosphonium salts such as tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, octylic acid tin and aluminum acetylacetone complex; Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, benzyltriethylammonium chloride; Boron compounds such as boron trifluoride and triphenyl borate; Metal halide compounds such as zinc chloride and tin tin; High melting point dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide, amine and adducts of epoxy resins; Microcapsule-type latent curing accelerators in which a surface of a curing accelerator such as an imidazole compound, an organophosphorus compound or a quaternary phosphonium salt is coated with a polymer; Amine salt type latent curing agent accelerators; Latent hardening accelerators, such as high-temperature dissociation-type thermocationic polymerization type latent hardening accelerators, such as a Lewis acid salt and a brendstead salt, etc. are mentioned.

Among them, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide (ethyltriphenylphosphonium bromide), and tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n -Quaternary ammonium salts, such as butylammonium chloride and benzyl triethylammonium chloride.

As a usage ratio of a catalyst, Preferably it is 100 mass parts or less with respect to 100 mass parts of polymers which have an epoxy group, More preferably, it is 0.01-100 mass parts, More preferably, it is 0.1-20 mass parts.

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

Reaction temperature becomes like this. Preferably it is 0-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

In this way, a solution containing a reaction product of a polymer having an epoxy group and a specific cinnamic acid derivative is obtained. This solution may be used as it is to prepare a cured film-forming composition, or after isolating the reaction product contained in the solution, and may be used to prepare the cured film-forming composition, or after purification of the isolated reaction product, forming a cured film. You may use for preparation of a composition.

<(B) component>

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

As a crosslinking agent which is (B) component, the compound which has 2 or more groups which form bridge | crosslinking with the heat crosslinkable functional group of the said (A) component is preferable, For example, it is a crosslinking agent which has 2 or more of methylol groups or an alkoxy methyl group. desirable. As a compound which has these groups, methylol compounds, such as the alkoxy methylation glycoluril, the alkoxy methylation benzoguanamine, and the alkoxy methylation melamine, are mentioned, for example.

As a specific example of the alkoxy methylation glycoluril, For example, 1,3,4,6- tetrakis (methoxymethyl) glycoluril, 1,3,4,6- tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1 , 3,3-tetrakis (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl ) -4,5-dimethoxy-2-imidazolinone etc. are mentioned. As a commercial item, compounds, such as a glycoluril compound (brand name: Cymel (trademark) 1170, Powder Link (trademark) 1174) by Japan Cytec Industries (former Mitsui Cytec Co., Ltd.), methylated urea resins ( Product Name: UFR (registered trademark) 65), Butylated urea resin (Product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd. Urea) / formaldehyde-based resin (high condensation type, trade name: becamine (registered trademark) J-300S, copper P-955, copper N), etc. may be mentioned.

Specific examples of the alkoxy methylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As a commercial item, Japan Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.) (brand name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (brand name: Nicarac (registered trademark) BX-4000 , BX-37, BL-60, BX-55H), and the like.

As a specific example of the alkoxy methylation melamine, hexamethoxy methyl melamine etc. are mentioned, for example. As a commercial item, methoxymethyl type melamine compound (former name: Cymel (registered trademark) 300, copper 301, copper 303, copper 350) made by Nippon Cytec Industries Co., Ltd. (former Mitsui Cytec Co., Ltd.), butoxymethyl Type melamine compound (a brand name: my coat (trademark) 506, copper 508), a methoxymethyl type melamine compound (brand name: Nicaraak (registered trademark) MW-30, copper MW-22, copper MW made by Sanwa Chemical Co., Ltd.) -11, same MS-001, same MX-002, same MX-730, same MX-750, same MX-035), butoxymethyl type melamine compound (brand name: Nicarac (registered trademark) MX-45, same MX) -410, the same MX-302), etc. are mentioned.

Moreover, the compound obtained by condensing the melamine compound, the urea compound, the glycoluril compound, and the benzoguanamine compound which the hydrogen atom of the amino group substituted by the methylol group or the alkoxy methyl group may be sufficient as a crosslinking agent. For example, a high molecular weight compound prepared from the melamine compound and the benzoguanamine compound described in the specification of US Pat. As a commercial item of the said melamine compound, a brand name: Cymel (trademark) 303 etc. are mentioned, As a commercial item of the said benzoguanamine compound, a brand name: Cymel (trademark) 1123 (above, Japan Cytec Industries) (Former Mitsui Cytec Co., Ltd. product) etc. are mentioned.

Furthermore, as a crosslinking agent of (B) component, hydroxymethyl groups, such as N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl methacrylamide ( That is, the polymer manufactured using the acrylamide compound or methacrylamide compound substituted by the methylol group) or the alkoxy methyl group can also be used.

Examples of such polymers include poly (N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, And copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.

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

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

The method of obtaining a polymer as mentioned above is not specifically limited. For example, the acrylic polymer which has a specific functional group is produced previously by superposition | polymerization methods, such as radical polymerization. Next, the polymerizable group containing C = C double bond is introduced into the polymer which is (B) component by making the specific functional group which an acrylic polymer has, and the compound which has an unsaturated bond at the terminal (henceforth a specific compound.) React. can do.

Here, a specific functional group means functional groups, such as a carboxyl group, a glycidyl group, a hydroxyl group, the amino group which has active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or multiple types of functional group selected from these.

In the above-mentioned reaction, the preferable combination of the specific functional group which an acrylic polymer has and the group which participates in reaction as a functional group which a specific compound has is a carboxyl group, an epoxy group, a hydroxyl group, an isocyanate group, a phenolic hydroxyl group, an epoxy group, and a carboxyl group Isocyanate group, an amino group, and an isocyanate group, or a hydroxyl group and an acid chloride group. Furthermore, a more preferable combination is an epoxy group in a carboxyl group and glycidyl methacrylate, or an isocyanate group in a hydroxyl group and an isocyanate ethyl methacrylate.

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

These crosslinking agents can be used individually or in combination of 2 or more types.

It is preferable that content of the crosslinking agent of (B) component in the cured film formation composition of this invention is 1 mass part-500 mass parts based on 100 mass parts of reaction products which are (A) component, More preferably, it is 5 mass parts It is 400 mass parts. When content of a crosslinking agent is too small, the solvent tolerance of the cured film obtained from a cured film formation composition falls, and liquid-crystal orientation falls. On the other hand, when content is excessive, liquid crystal orientation and storage stability may fall.

<(C) component>

The cured film formation composition of this invention may contain the polymer which has at least 1 group chosen from the group which consists of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxy silyl group as (C) component.

As a polymer which is (C) component, acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone Polymers having a linear or branched structure such as polyols, polyalkyleneimines, polyallylamines, celluloses (celluloses or derivatives thereof), phenol novolac resins, melamine formaldehyde resins, and cyclic polymers such as cyclodextrins. Can be mentioned.

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

As an acrylic polymer which is a preferable example of the polymer of (C) component, it is a polymer obtained by superposing | polymerizing the monomer which has unsaturated double bonds, such as acrylic acid, methacrylic acid, styrene, and a vinyl compound, and has specific functional group 2 [hydroxy group, a carboxyl group, A polymer obtained by polymerizing a monomer containing a monomer having a group selected from the group consisting of an amide group, an amino group alkoxysilyl group and a group represented by the following formula (2) or a mixture thereof may be used as a polymer constituting an acrylic polymer. It does not specifically limit about the skeleton of a main chain, the kind of side chain, etc.

Examples of the monomer having a specific functional group 2 include a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxyl group, a monomer having a carboxyl group, a monomer having an amino group, and alkoxysilyl Monomer which has a group, and following formula (2)

[Formula 3]

In the formula, a monomer having a group represented by R ⁴¹ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a phenyl group.

A monomer having the above-mentioned polyethylene glycol, there may be mentioned a monoacrylate or monomethacrylate of _{H- (OCH 2 CH 2) n} -OH. The value of n is 2-50, Preferably it is 2-10.

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

As a monomer which has the above-mentioned phenolic hydroxyl group, p-hydroxy styrene, m-hydroxy styrene, o-hydroxy styrene is mentioned, for example.

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

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

As a monomer which has the alkoxysilyl group mentioned above, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryl, for example. Oxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and the like.

In the formula (2), examples of the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms in R ⁴¹ include a group having the corresponding carbon atom number in the alkyl group or alkoxy group exemplified above.

As a monomer which has group represented by Formula (2) mentioned above, the monomer etc. which have group represented by the following formula [2-1]-[2-5] are mentioned, for example.

[Formula 4]

In addition, in this embodiment, in synthesizing the acrylic polymer which is an example of (C) component, unless it is impairing the effect of this invention, a hydroxyl group, a carboxyl group, an amide group, an amino group, the alkoxy silyl group, and the said formula ( The monomer which does not have any of the group represented by 2) can be used together.

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

As an acrylate ester compound, For example, 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-methoxy ethyl acrylate, methoxy triethylene glycol acrylate, 2- ethoxy ethyl acrylate, Tetrahydrofurfurylacrylate, 3-methoxybutylacrylate, 2-methyl-2-adamantylacrylate, 2-propyl-2-adamantylacrylate, 8-methyl-8-tricyclodecylacrylate And 8-ethyl-8-tricyclodecyl acrylate.

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

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

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

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

It is preferable that the usage-amount of the monomer which has a specific functional group 2 used in order to obtain the acrylic polymer which is an example of (C) component is 2 mol% or more based on the total amount of all the monomers used in order to obtain the acrylic polymer which is (C) component. When the monomer which has the specific functional group 2 is too small, the solvent resistance of the cured film obtained is easy to become inadequate.

Although the method of obtaining the acrylic polymer which is an example of (C) component is not specifically limited, For example, the monomer containing the monomer which has a specific functional group 2, the monomer which does not have a specific functional group 2 as needed, a polymerization initiator, etc. coexist. In the solvent made above, it is obtained by a polymerization reaction at a temperature of 50 ° C to 110 ° C. At this time, the solvent used will not be specifically limited if it melt | dissolves the monomer which has a specific functional group 2, the monomer which does not have a specific functional group 2 used as needed, a polymerization initiator, etc. As a specific example, it describes in the term of the [solvent] mentioned later.

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

In addition, the solution of the acrylic polymer which is an example of (C) component obtained by the said method is thrown into diethyl ether, water, etc. under stirring, and reprecipitated, and the produced precipitate is filtered and washed, and normal temperature drying or under reduced pressure or It can heat-dry and can be set as the powder of the acrylic polymer which is an example of (C) component. By the above-mentioned operation, the polymerization initiator and unreacted monomer which coexist with the acrylic polymer which is an example of (C) component can be removed, As a result, the powder of the acrylic polymer which is an example of the refined (C) component is obtained. When it cannot fully refine | purify by operation once, the obtained powder may be re-dissolved in a solvent and the above-mentioned operation may be repeated.

It is preferable that the weight average molecular weights are 3000-200000, as for the acrylic polymer which is a preferable example of (C) component, it is more preferable that it is 4000-150000, It is still more preferable that it is 5000-100000. If the weight average molecular weight is more than 200000, the solubility in the solvent may be lowered and the handling properties may be lowered. If the weight average molecular weight is less than 3000, the curing resistance may be insufficient at the time of thermosetting, and the solvent resistance may be reduced. It may fall. In addition, a weight average molecular weight is a value obtained by using polystyrene as a standard sample by gel permeation chromatography (GPC). Hereinafter, it is the same also in this specification.

Next, as a polyether polyol which is a preferable example of the polymer of (C) component, Polypropylene glycol, a polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, sorbitol, etc. are polypropylene alcohol, polyethylene glycol, polypropylene The thing which added glycol etc. is mentioned. Specific examples of the polyether polyol include ADEKA Adeka Polyether P Series, G Series, EDP Series, BPX Series, FC Series, CM Series, Nichi Oil Uniox® HC-40, HC-60, ST- 30E, ST-40E, G-450, G-750, Uniol® 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 etc. are mentioned.

As polyester polyol which is a preferable example of the polymer of (C) component, Diol, such as ethylene glycol, a propylene glycol, butylene glycol, polyethyleneglycol, polypropylene glycol, in polyhydric carboxylic acids, such as adipic acid, sebacic acid, and isophthalic acid The thing which reacted is mentioned. As a specific example of polyester polyol, DIC polylite (trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X- 668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD-X-2555, OD-X-2560, Kuraray Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F- 1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc. are mentioned.

As polycaprolactone polyol which is a preferable example of the polymer of (C) component, the thing which ring-opened-polymerized (epsilon) -caprolactone with polyhydric alcohols, such as trimethylol propane and ethylene glycol, as an initiator is mentioned. As a specific example of polycaprolactone polyol, DIC polylite (trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Fraxel (trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc. are mentioned.

As polycarbonate polyol which is a preferable example of the polymer of (C) component, what reacted polyhydric alcohols, such as trimethylol propane and ethylene glycol, with diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. is mentioned. Specific examples of the polycarbonate polyol include Daicel Fraxel CD205, CD205PL, CD210, CD220, Cura590, C-1050, C-2050, C-2090, C-3090, etc. have.

As cellulose which is a preferable example of the polymer of (C) component, hydroxyalkyl celluloses, such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, etc. Hydroxyalkyl alkyl celluloses, cellulose, and the like, for example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

As cyclodextrins which are a preferable example of the polymer of (C) component, Cyclodextrins, such as (alpha)-cyclodextrin, (beta) -cyclodextrin, and (gamma)-cyclodextrin, methyl- (alpha)-cyclodextrin, methyl- (beta)-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-hydroxypropyl-γ -Cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin , And hydroxyalkylcyclodextrins such as 2,3-dihydroxypropyl-β-cyclodextrin and 2,3-dihydroxypropyl-γ-cyclodextrin.

Melamine formaldehyde resin which is a preferable example of the polymer of (C) component is resin obtained by polycondensing melamine and formaldehyde.

It is preferable that the methylol group produced | generated at the time of the polycondensation of melamine and formaldehyde has alkylated the melamine formaldehyde resin of (C) component, As such a melamine formaldehyde resin, it is a following formula, for example. The compound represented by these is mentioned.

[Formula 5]

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

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

It is preferable that the weight average molecular weights of melamine formaldehyde resin of (C) component are 250-5000, It is more preferable that it is 300-4000, It is still more preferable that it is 350-3500. If the weight average molecular weight is more than 5000, the solubility in the solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 250, the curing resistance may be insufficient at the time of thermosetting, and the solvent resistance may be reduced. In some cases, the improvement effect may not be sufficiently exhibited.

In embodiment of this invention, melamine formaldehyde resin of (C) component may be a liquid form, or you may use it in the form of the solution which melt | dissolved the refined liquid in the solvent mentioned later.

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

In the cured film formation composition of this embodiment, the polymer of (C) component may be powder form, or you may use it in the form of the solution which melt | dissolved the refined powder in the solvent mentioned later.

In addition, in the cured film formation composition of this embodiment, the mixture of multiple types of the polymer illustrated as (C) component may be sufficient as (C) component.

Content of (C) component in the cured film formation composition of this invention is 400 mass parts or less normally with respect to 100 mass parts which is the total amount of the reaction product which is (A) component, and the crosslinking agent of (B) component, Preferably 1-400 mass parts, More preferably, they are 10 mass parts-380 mass parts, More preferably, they are 40 mass parts-360 mass parts. When content of (C) component is excessive, liquid-crystal orientation will fall easily.

<(D) component>

The cured film formation composition of this invention can contain a crosslinking catalyst further as (D) component in addition to the said (A) component and (B) component.

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

Specific examples of the component (D) include sulfonic acid group-containing compounds, hydrochloric acid or salts thereof. The thermal acid generator is not particularly limited as long as it is a compound that generates acid by thermal decomposition during heat treatment, that is, a compound that generates acid by thermal decomposition at a temperature of 80 ° C to 250 ° C.

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

Moreover, as a compound which generate | occur | produces an acid by heat, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylenetris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluene Sulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p Toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and a compound represented by the following formula:

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

Etc. can be mentioned.

Content of (D) component in the cured film formation composition of this invention becomes like this. Preferably it is 0.01 mass part-20 mass with respect to 100 mass parts which is the total amount of the reaction product which is (A) component, and the crosslinking agent of (B) component. Part, More preferably, it is 0.1 mass part-15 mass parts, More preferably, it is 0.5 mass part-10 mass parts. By making content of (D) component into 0.01 mass part or more, sufficient thermosetting and solvent resistance can be provided. However, when more than 20 mass parts, the storage stability of a composition may fall.

<(E) component>

This invention can also contain the component (henceforth an adhesive improvement component.) Which improves the adhesiveness of the cured film formed as (E) component.

When using the cured film formed from the cured film formation composition of this embodiment containing (E) component as an orientation material, so that the adhesiveness of the layer of an orientation material and a polymeric liquid crystal may improve so that the polymeric functional group of a polymeric liquid crystal and an orientation material may be improved. The crosslinking site can be linked by covalent bonds. As a result, the phase difference material of this embodiment which laminated | stacked the polymeric liquid crystal hardened | cured on the orientation material of this embodiment can maintain strong adhesiveness even under high temperature, high quality conditions, and can exhibit high durability with respect to peeling etc. .

As the component (E), at least one group A selected from the group consisting of at least one polymerizable group, a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or at least one group reacting with this group A The compound which has can be used.

As the component (E), monomers and polymers having a group selected from a hydroxy group and an N-alkoxymethyl group, a polymerizable group are preferable.

As such (E) component, the compound which has a hydroxyl group (meth) acryl group, the compound which has N-alkoxy methyl group (meth) acryl group, the polymer which has N-alkoxy methyl group (meth) acryl group, etc. are mentioned. Hereinafter, specific examples are shown, respectively.

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

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

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

[Formula 12]

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

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

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

The N, i.e., nitrogen atom of the N-alkoxymethyl group is a nitrogen atom of amide, a nitrogen atom of thioamide, a nitrogen atom of urea, a nitrogen atom of thiourea, a nitrogen atom of urethane, or a nitrogen bonded to a nitrogen atom of a nitrogen-containing heterocyclic ring Atom etc. are mentioned. Therefore, as the N-alkoxymethyl group, the nitrogen atom of the amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, the nitrogen atom bonded to the adjacent position of the nitrogen atom of nitrogen-containing heterocyclic ring, etc. The structure which the alkoxy methyl group couple | bonded with the selected nitrogen atom is mentioned.

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

[Formula 13]

(In formula, R <^31> represents a hydrogen atom or a methyl group, R <^32> represents a hydrogen atom or a linear or branched alkyl group of 1-10 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, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1 , 2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n -Hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2- Ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl- 3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, etc. are mentioned.

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

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

[Formula 14]

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

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

R ⁵³ represents a divalent aliphatic group including a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms, and an ether in the structure It may also include a combination.

R ⁵⁴ is a linear or branched C 2 -C 9 aliphatic group having 1 to 20 carbon atoms, C 2 -C 6 divalent aliphatic ring group, or C 2 -C 6 aliphatic ring containing 5 to 6 carbon atoms It may represent an aliphatic group of 9 to 9, and one of these groups or a plurality of non-neighboring methylene groups may be substituted with an ether bond.

Z represents> NCOO- or -OCON <(where "-" represents one bond. In addition, ">""<" represents two bonds and any one bond is an alkoxymethyl group ( That is, combined with -OR ⁵² group).

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

As a specific example of the C2-C20 alkylene group in the definition of R <^53>, the bivalent group remove | excluding one hydrogen atom further from the C2-C20 alkyl group is mentioned.

Moreover, as a specific example of the bivalent to 9-valent aliphatic group of 1-20 carbon atoms in the definition of R <^54>, the divalent-9 is remove 1-8 hydrogen atoms further from the alkyl group of 1-20 carbon atoms. Can be mentioned.

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, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, n- Hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1,1,2-trimethyl-n -Propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n- tetradecyl group, n-pentadede Real group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-ecosyl group, cyclopentyl group, cyclohexyl group, 1 or more of these to 20 carbon atoms The group couple | bonded in the range of and the methylene group of these groups, or the group by which the some methylene group which does not adjoin is substituted by the ether bond etc. are mentioned as an example.

Among these, an alkylene group having 2 to 10 carbon atoms is preferable, and R ⁵³ is an ethylene group, and R ⁵⁴ is particularly preferably a hexylene group in view of availability of raw materials.

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

As r, the natural number of 2 or more and 9 or less is mentioned, Especially, the natural number of 2-6 is preferable.

Content of (E) component in the cured film formation composition of embodiment of this invention becomes like this. Preferably it is 1 mass part with respect to 100 mass parts which is the total amount of the reaction product which is (A) component, and the crosslinking agent of (B) component. It is -100 mass parts, More preferably, it is 5 mass parts-70 mass parts. Sufficient adhesiveness can be provided to the cured film formed by making content of (E) component 1 mass part or more. However, when more than 100 mass parts, liquid crystal orientation will fall easily.

In addition, in the cured film formation composition of this embodiment, the mixture of multiple types of the compound of (E) component may be sufficient as (E) component.

<Solvent>

The cured film formation composition of this invention is mainly used in the solution state melt | dissolved in the solvent. The solvent used at this time should just melt | dissolve (A) component, (B) component, and if necessary, (C) component, (D) component, (E) component, and / or the other additive mentioned later, and the kind And structures are not particularly limited.

As a specific example of a solvent, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1- butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentane On, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate Ethyl hydroxy acetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, pyruvic acid Ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentylmethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like. .

When the cured film is formed on the resin film using the cured film-forming composition of the present invention to produce an alignment material, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol, 2 Heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, cyclopentylmethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate and the like are solvents in which the resin film exhibits resistance It is preferable at the point.

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

<Other additives>

Furthermore, as long as the effect of this invention is not impaired, the cured film formation composition of this invention is an adhesive improving agent, a silane coupling agent, surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoamer, Antioxidants and the like.

<Preparation of the cured film forming composition>

The cured film formation composition of this invention contains the reaction product of (A) component, and the crosslinking agent of (B) component, and if necessary, the polymer of (C) component, the crosslinking catalyst of (D) component, and (E) component Compounds, and further compositions that may contain other additives so long as the effects of the present invention are not impaired. And usually, they are used as a form of the solution which melt | dissolved in the solvent.

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

[1]: Cured film formation composition containing 1 mass part-500 mass parts (B) component based on (A) component and 100 mass parts of (A) component.

[2]: Based on (A) component and 100 parts by mass of component (A), 1 part by mass to 500 parts by mass of component (B), and the total amount of a reaction product and a crosslinking agent of component (B) Cured film formation composition containing 1-400 mass parts (C) component with respect to 100 mass parts of phosphorus.

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

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

[5]: 100 based on (A) component and 100 parts by mass of component (A), 100 parts by mass of (B) component, reaction product which is (A) component, and total amount of crosslinking agent of component (B) 0.01 parts by mass to 20 parts by mass of (D) component with respect to 100 parts by mass of 100 parts by mass of the crosslinking agent of the component (C), the reaction product (A) and the component (A), 1 to 400 parts by mass, and Cured film formation composition containing a solvent.

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

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

Although the ratio of solid content in the cured film formation composition of this invention is not specifically limited as long as each component is melt | dissolving uniformly in a solvent, It is 1 mass%-60 mass%, Preferably it is 2 mass%-50 It is mass%, More preferably, it is 2 mass%-20 mass%. Here, solid content removes the solvent from all the components of a cured film formation composition.

The preparation method of the cured film formation composition of this invention is not specifically limited. As a preparation method, for example, (B) component, Furthermore, (C) component, (D) component, (E) component, etc. are mixed with the solution of (A) component melt | dissolved in the solvent in predetermined ratio, and it is uniform The method of making it into one solution, or the method of mixing and adding another additive further as needed in the suitable step of this preparation method.

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

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

<Cured film, alignment material, and phase difference material>

The solution of the cured film-forming composition of the present invention may be a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc., a glass substrate, or a quartz substrate). , ITO substrate, etc.) or a film substrate (for example, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET)) A film, acrylic film, resin film such as polyethylene film), etc., by coating with a bar coat, rotary coating, shedding coating, roll coating, slit coating, slit followed by rotary coating, inkjet coating, printing, etc. Then, the cured film can be formed by heat-drying with a hotplate, oven, etc. This cured film can be applied as an orientation material as it is.

As conditions for heat drying, the crosslinking reaction by a crosslinking agent should just advance so that the component of a cured film (orientation material) may not elute in the polymeric liquid crystal solution apply | coated on it, for example, temperature 60 degreeC-200 The heating temperature and heating time suitably selected from the range of 0, C and 0.4 minutes-60 minutes are employ | adopted. Heating temperature and a heat time become like this. Preferably they are 70 degreeC-160 degreeC, and 0.5 minute-10 minutes.

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

Since the alignment material formed from the cured film composition of this invention has solvent resistance and heat resistance, retardation materials, such as the polymeric liquid crystal solution which has a vertical alignment property, can be apply | coated on this alignment material, and it can orientate on an alignment 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 retardation film.

Moreover, using two board | substrates which have the orientation material of this invention formed as mentioned above, bonding together the orientation materials on both board | substrates through a spacer, and inject | pouring a liquid crystal between these board | substrates, a liquid crystal It can also be set as this aligned liquid crystal display element.

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

Example

Hereinafter, although an Example of this invention is given and this invention is demonstrated concretely, this invention is not limited to these and is interpreted.

[Abbreviated sign used in the embodiment]

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

<Raw material>

GMA: glycidyl methacrylate

M100: 3,4-epoxycyclohexylmethyl methacrylate

AIBN: α, α'-azobisisobutyronitrile

BMAA: N-butoxymethylacrylamide

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

<Component B>

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

[Formula 15]

PL: tetramethoxymethylglycoluril [POWDERLINK (registered trademark) 1174 (made by Mitsui Cytec Co., Ltd.)]

[Formula 16]

<D component>

PTSA: p-toluenesulfonic acid monohydrate

<E component>

E-1: the compound which has a hydroxyl group and an acryl group represented by the following structural formula

[Formula 17]

E-2: a compound having an N-alkoxymethyl group and an acryl group represented by the following structural formula

[Formula 18]

<Solvent>

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

<Measurement of molecular weight of polymer>

The molecular weight of the acrylic copolymer in the polymerization example is as follows using a room temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Shodex Corporation, and a column (KD-803, KD-805) manufactured by Shodex Corporation. It was measured by.

In addition, the following number average molecular weight (henceforth Mn) and a weight average molecular weight (henceforth Mw) were shown by polystyrene conversion value.

Column temperature: 40 ℃

Eluent: tetrahydrofuran

Flow rate: 1.0mL / min

Standard sample for calibration curve preparation: Standard polystyrene made by Showa Denko Co., Ltd. (molecular weight: about 197,000, 55,100, 12,800, 3,950, 1,260, 580).

<Synthesis of A component>

<Polymerization Example 1>

An acrylic polymer solution was obtained by dissolving 0.5 g of AIBN in 46.4 g of tetrahydrofuran as a GMA 15.0 g and a polymerization catalyst and reacting for 20 hours under reflux. The obtained acrylic polymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, followed by filtration and drying under reduced pressure, thereby obtaining an acrylic polymer (P1) having an epoxy group. Mn of the obtained acrylic polymer was 25,000 and Mw was 9,800.

<Polymerization Example 2>

15.0 g of M100 and 0.5 g of AIBN were dissolved in 46.4 g of tetrahydrofuran as a polymerization catalyst, and an acrylic polymer solution was obtained by reacting for 20 hours under reflux. The obtained acrylic polymer solution was slowly added dropwise to 500.0 g of hexane to precipitate a solid, followed by filtration and drying under reduced pressure, thereby obtaining an acrylic polymer (P2) having an epoxy group. Mn of the obtained acrylic polymer was 35,000 and Mw was 15,000.

Synthesis Example 1

10.0 g of acrylic polymer (P1) having an epoxy group obtained in Polymerization Example 1, 11.3 g of 4-methoxy cinnamic acid, and 0.4 g of benzyltriethylammonium chloride were dissolved in 50.8 g of PM as a reaction catalyst and reacted at 120 ° C. for 20 hours. The solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, and the polymer (PA-1) was obtained by filtration and drying under reduced pressure. The epoxy value of the obtained polymer was measured and it confirmed that the epoxy group was lost.

Synthesis Example 2

10.0 g of acrylic polymer (P1) having an epoxy group obtained in Polymerization Example 1, 12.0 g of 4-propoxycyanic acid, and 0.4 g of benzyltriethylammonium chloride were dissolved in 50.8 g of PM as a reaction catalyst and reacted at 120 ° C for 20 hours. The solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, and the polymer (PA-2) was obtained by filtration and drying under reduced pressure. The epoxy value of the obtained polymer was measured and it confirmed that the epoxy group was lost.

Synthesis Example 3

10.0 g of acrylic polymer (P1) having an epoxy group obtained in Polymerization Example 1, 14.5 g of 3- (1,1'-biphenyl-4-yl) acrylic acid, and 0.4 g of benzyltriethylammonium chloride as a reaction catalyst were added to 58.8 g of PM. It melt | dissolved and made it react at 120 degreeC for 20 hours. The solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, and the polymer (PA-3) was obtained by filtration and drying under reduced pressure. The epoxy value of the obtained polymer was measured and it confirmed that the epoxy group was lost.

Synthesis Example 4

10.0 g of acrylic polymer (P2) having an epoxy group obtained in Polymerization Example 2, 8.2 g of 4-methoxy cinnamic acid, and 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 43.2 g of PM and reacted at 120 ° C. for 20 hours. The solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, and the polymer (PA-4) was obtained by filtration and drying under reduced pressure. The epoxy value of the obtained polymer was measured and it confirmed that the epoxy group was lost.

Synthesis Example 5

10.0 g of polymer UG-4035 (ARUFON series manufactured by Dong-A Synthetic Co., Ltd.) having epoxy group, 3.1 g of 4-methoxy cinnamic acid, 0.1 g of benzyltriethylammonium chloride as a reaction catalyst was dissolved in 52.7 g of PM, and 20 at 120 ° C. The reaction was time. The solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, and the polymer (PA-5) was obtained by filtration and drying under reduced pressure. The epoxy value of the obtained polymer was measured and it confirmed that the epoxy group was lost.

Synthesis Example 6

10.0 g of polymer EHPE3150 (manufactured by Daicel Co., Ltd.) having an epoxy group, 9.9 g of 4-methoxy cinnamic acid, and 0.4 g of benzyltriethylammonium chloride were dissolved in 47.2 g of PM as a reaction catalyst and reacted at 120 ° C for 20 hours. The solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, and the polymer (PA-6) was obtained by filtration and drying under reduced pressure. The epoxy value of the obtained polymer was measured and it confirmed that the epoxy group was lost.

Synthesis Example 7

10.0 g of polymer ECN-1299 (manufactured by Asahi Kasei Co., Ltd.) having an epoxy group, 10.3 g of 4-methoxy cinnamic acid, and 0.3 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 61.9 g of PM and reacted at 120 ° C. for 20 hours. I was. This solution was slowly added dropwise to 700 g of diethyl ether to precipitate a solid, and the polymer (PA-7) was obtained by filtration and drying under reduced pressure. The epoxy value of the obtained polymer was measured and it confirmed that the epoxy group was lost.

Synthesis Example 8

10.0 g of acrylic polymer (P1) having an epoxy group obtained in Polymerization Example 1, 7.3 g of 4-methoxy cinnamic acid, 1.3 g of acrylic acid, 0.2 g of dibutylhydroxytoluene, and 0.2 g of ethyltriphenylphosphonium bromide as a reaction catalyst were PM 44.6. It dissolved in g and made it react at 90 degreeC for 20 hours. This solution was slowly added dropwise to 500 g of diethyl ether to precipitate a solid, and the polymer (PA-8) was obtained by filtration and drying under reduced pressure. The epoxy value of the obtained polymer was measured and it confirmed that the epoxy group was lost. The ratio of the thing which reacted with 4-methoxy cinnamic acid in the epoxy group of this polymer (PA-8) is 70 mol%.

<Synthesis of B component>

<Polymerization Example 3>

100.0 g of BMAA and 4.2 g of AIBN were dissolved in 193.5 g of PM as a polymerization catalyst, and an acrylic polymer solution was obtained by reacting at 90 ° C for 20 hours. The acrylic polymer solution was slowly added dropwise to 2000.0 g of hexane to precipitate a solid, and the polymer (PB-1) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic polymer was 2,700 and Mw was 3,900.

<Polymerization Example 4>

An acrylic copolymer solution was obtained by dissolving 0.8 g of AIBN in 204.0 g of tetrahydrofuran as a BMAA 32.0 g, 8.0 g of GMA, and a polymerization catalyst, and reacting at 60 ° C for 20 hours. The acrylic copolymer solution was slowly added dropwise to 1000.0 g of hexane to precipitate a solid, and the acrylic copolymer (P-3) was obtained by filtration and drying under reduced pressure. Mn of the obtained acrylic copolymer was 7,000 and Mw was 18,000.

Synthesis Example 9

10.0 g of acrylic copolymer (P-3) obtained in Polymerization Example 4, 2.2 g of acrylic acid, 0.2 g of dibutylhydroxytoluene, and 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM and reacted at 90 ° C. for 20 hours. I was. The solution was slowly added dropwise to 500 g of hexane to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PB-2) having an acroyl group. ¹ H-NMR analysis was conducted to confirm that the polymer (PB-2) had an acroyl group.

<Synthesis of C component>

<Polymerization Example 5>

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

<Preparation of polymerizable liquid crystal solution>

<Preparation Example 1>

Solid content concentration was added by adding 29.0 g of polymerizable liquid crystal LC242 (made by BASF), 0.9 g of Monocure 907 (made by BASF) as a polymerization initiator, 0.2 g of BYK-361N (manufactured by BYK) as a leveling agent, and methyl isobutyl ketone as a solvent. The polymeric liquid crystal solution (RM-1) which is mass% was obtained.

<Preparation Example 2>

Solid content concentration was added by adding 29.0 g of polymerizable liquid crystal LC242 (manufactured by BASF Corporation), 0.9 g of Monocure 907 (manufactured by BASF Corporation) as a polymerization initiator, 0.2 g of BYK-361N (manufactured by BYK Corporation) as a leveling agent, and CP (cyclopentanone) as a solvent. The polymerizable liquid crystal solution (RM-2) having 30 mass% was obtained.

<Example, Comparative Example>

Each cured film formation composition of an Example and a comparative example was prepared with the composition shown in Table 1. Next, the cured film was formed using each cured film formation composition, and the orientation property was evaluated about each obtained cured film.

[Evaluation of Orientation]

Each cured film formation composition of an Example and a comparative example was apply | coated on the TAC film by 4 micrometers of Wet film thickness using the bar coater. Heat-drying was performed in a thermocyclic oven for 60 second at the temperature of 90 degreeC or 110 degreeC, respectively, and the cured film formed on the TAC film, respectively. 313 nm linearly polarized light was irradiated perpendicularly to each cured film by the exposure amount of ⁵ mJ / cm <^2> or 30mJ / cm <^2> , and the orientation material was formed. On the alignment material on a TAC film, polymeric liquid crystal solution (RM-1) or (RM-2) was apply | coated to the Wet film thickness of 6 micrometers using the bar coater. This coating film was dried for 60 second on the hotplate of temperature 90 degreeC, and then exposed at 300mJ / cm <^2> , and the phase difference material was produced. Insert the phase difference material on the produced board | substrate into a pair of polarizing plate, observe the expression state of the phase difference characteristic in a phase difference material, and let the thing which phase difference was expressed without defect and o that the phase difference was not expressed as "Orientation" It is described in the column. The evaluation results are summarized in Table 2 later.

As shown in Table 2, the phase difference material obtained using the cured film formation composition of Examples 1-18 showed the favorable liquid crystal orientation even in the polarization exposure amount 5mJ / cm <^2> .

On the other hand, the retardation material obtained using the cured film formation composition of Comparative Examples 1-3 was not able to acquire favorable liquid-crystal orientation even in the polarization exposure amount 30mJ / cm <^2> .

Industrial availability

The cured film formation composition by this invention is very useful as a material which forms the orientation material for forming the liquid crystal aligning film of a liquid crystal display element, or the optically anisotropic film provided in an inside or the exterior in a liquid crystal display element, Especially, IPS- It is suitable as a material for phase difference of a circularly polarizing plate used as an antireflection film of LCD or organic EL display.

Claims (12)

(A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative represented by the following formula (1), and
(B) Cross-linking system
Cured film formation composition containing the.
[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, a haloalkyl group having 1 to 6 carbon atoms, A cycloalkyl group having 3 to 8 carbon atoms, a halocycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, and a carbon atom Halocycloalkenyl groups having 3 to 8 carbon atoms, alkynyl groups having 2 to 6 carbon atoms, haloalkynyl groups having 2 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, haloalkoxy groups having 1 to 6 carbon atoms, and (carbon atoms) 1-6 alkyl) 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 and (1 to 6 carbon atoms) Alkylamino) carbonyl group, (haloalkyl having 1 to 6 carbon atoms) aminocarbonyl group, di (with 1 to 6 carbon atoms) An alkyl) aminocarbonyl group, a cyano group, and a substituent selected from the group consisting of nitro groups, R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group, and R ³ is a A bond, an oxygen atom, -COO- or -OCO-, and R ⁴ to R ⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and 1 carbon atom A substituent selected from the group consisting of alkoxy group of ˜6, haloalkoxy group of 1 to 6 carbon atoms, cyano group, and nitro group, and n is an integer of 0 to 3.) The method of claim 1,
The cured film formation composition whose (B) crosslinking agent is a crosslinking agent which has a methylol group or the alkoxy methyl group. The method according to claim 1 or 2,
(C) Cured film formation composition which further contains the polymer which has at least 1 group chosen from the group which consists of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. The method according to any one of claims 1 to 3,
(D) Cured film formation composition which further contains a crosslinking catalyst. The method according to any one of claims 1 to 4,
(E) Contain a compound having at least one polymerizable group and at least one group A selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group or at least one group reacting with this group A Cured film formation composition. The method according to any one of claims 1 to 5,
The cured film formation composition containing 1 mass part-500 mass parts (B) component based on 100 mass parts of (A) component. The method according to any one of claims 3 to 6,
Cured film formation composition containing 1 mass part-400 mass parts (C) component with respect to 100 mass parts which is a total amount of (A) component and (B) component. The method according to any one of claims 4 to 7,
Cured film formation composition containing 0.01 mass part-20 mass parts (D) component with respect to 100 mass parts which is a total amount of (A) component and (B) component. The method according to any one of claims 5 to 8,
Cured film formation composition containing 1 mass part-100 mass parts (E) component with respect to 100 mass parts which is a total amount of (A) component and (B) component. The cured film obtained using the cured film formation composition of any one of Claims 1-9. The orientation material formed using the cured film formation composition of any one of Claims 1-9. Retardation material which has a cured film obtained using the cured film formation composition of any one of Claims 1-9.