JPWO2019027045A1 - Hardened film forming composition, alignment material and retardation material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured film forming composition for providing an alignment material showing good liquid crystal orientation and excellent adhesion to a liquid crystal layer. SOLUTION: A cured film-forming composition containing (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond and (B) a cross-linking agent, and obtained from the same. Hardened film, alignment material, and retardation material. [Selection diagram] None

Description

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

In the case of a circularly polarized glasses type 3D display, a retardation material is usually arranged on a display element such as a liquid crystal panel that forms an image. In this retardation material, a plurality of two types of retardation regions having different retardation characteristics are regularly arranged to form a patterned retardation material. Hereinafter, in the present specification, a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

The patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal, as disclosed in Patent Document 1. Optical patterning of a retardation material composed of a polymerizable liquid crystal utilizes a photoalignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-oriented material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photoalignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different orientation control directions of the liquid crystal are formed. A solution-like retardation material containing a polymerizable liquid crystal is applied onto the photoalignment film to realize the orientation of the polymerizable liquid crystal. Then, 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 1/4 wavelength retardation plate, and the external light directed to the panel surface of the image display panel is converted into linearly polarized light by the linear polarizing plate, followed by 1/4 wavelength. It is converted to circularly polarized light by the retardation plate. Here, the external light due to this circular polarization is reflected by the surface of the image display panel or the like, but the rotation direction of the polarized surface is reversed during this reflection. As a result, the reflected light is converted from the 1/4 wavelength retardation plate into linearly polarized light in the direction shaded by the linear polarizing plate, and then shielded by the subsequent linear polarizing plate, which is the opposite of the light reflected at the time of arrival. As a result, the emission to the outside is remarkably suppressed.

Regarding this 1/4 wavelength retardation plate, Patent Document 2 describes that the optical film has reverse dispersion characteristics by forming a 1/4 wavelength retardation plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate. The method of constructing by is proposed. In the case of this method, in a wide wavelength band used for displaying a color image, a liquid crystal material having a positive dispersion characteristic can be used to form an optical film having a reverse dispersion characteristic.

Further, in recent years, as a liquid crystal material applicable to this retardation layer, a material having a reverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such a reverse dispersion characteristic, instead of forming the 1/4 wavelength retardation plate by combining the 1/2 wavelength plate and the 1/4 wavelength plate to form the 1/4 wavelength retardation plate by the two retardation layers, the retardation layer Can be configured with a single layer to ensure inverse dispersion characteristics, whereby an optical film capable of securing a desired phase difference in a wide wavelength band can be realized with a simple configuration.

An alignment layer is used to orient the liquid crystal. For example, a rubbing method and a photo-alignment method are known as methods for forming an alignment layer. The photo-alignment method does not generate static electricity or dust, which is a problem of the rubbing method, and can quantitatively control the orientation process. Is useful in.

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

In addition to the liquid crystal alignment ability, the alignment layer is required to have adhesion to the liquid crystal layer. For example, if the adhesion between the alignment layer and the liquid crystal layer formed on the alignment layer is insufficient, the liquid crystal layer may be peeled off in the winding step or the like included in the production of the retardation film.

Japanese Unexamined Patent Publication No. 2005-49965 Japanese Unexamined Patent Publication No. 10-68816 U.S. Pat. No. 8119026 JP-A-2009-179563 Japanese Patent No. 361342 JP-A-2009-058584 Special Table 2001-517719

An object of the present invention has been made based on the above findings and examination results. That is, an object of the present invention is to provide a cured film-forming composition for providing an alignment material that exhibits good liquid crystal orientation and has excellent adhesion to a liquid crystal layer.

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

As a result of intensive studies to achieve the above object, the present inventors have obtained (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, (B). We have found that by selecting a cured film-forming composition based on a cross-linking agent, it is possible to form a cured film showing good liquid crystal orientation and excellent adhesion to the liquid crystal layer, and completed the present invention.

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

As a second aspect, the cured film-forming composition according to the first aspect, wherein the group containing the polymerizable double bond is a (meth) acryloyl group.

式（１）中、Ａ^１とＡ^２はそれぞれ独立に、水素原子またはメチル基を表し、
Ｒ^１は下記式（ｃ−２）

（式（ｃ−２）中、破線は結合手を表し、Ｒ^１０１は炭素数１〜３０のアルキレン基を表し、このアルキレン基の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ^１０１中の−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−に置き換えられていてもよく、さらに、次に挙げるいずれかの基が互いに隣り合わない場合において、−Ｏ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、−ＮＨＣＯＮＨ−及び−ＣＯ−からなる群から選ばれる基に置き換えられていてもよく、Ｍ^１は水素原子又はメチル基を表す。）で表される基を表し、
Ｒ^２は２価の芳香族基、２価の脂環族基、２価の複素環式基または２価の縮合環式基を表し、
Ｒ^３は単結合、酸素原子、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨＣＯＯ−または−ＯＣＯＣＨ＝ＣＨ−を表し、
Ｒ^４〜Ｒ^７はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数１〜６のハロアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のハロアルコキシ基、シアノ基、及びニトロ基からなる群から選ばれる置換基を表し、
また、Ｒ^２、Ｒ^３及びＲ^４又はＲ^２、Ｒ^３及びＲ^６は一緒になって芳香族基を形成してもよく、
ｎは０〜３の整数である。）As a third aspect, the cured film-forming composition according to the first aspect or the second aspect, wherein the cinnamic acid derivative having a group containing a polymerizable double bond is a compound represented by the following formula (1).

In formula (1), A ¹ and A ² independently represent a hydrogen atom or a methyl group, respectively.
R ¹ is the following formula (c-2)

(In the formula (c-2), the broken line represents a bond, R ¹⁰¹ represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group are replaced with a fluorine atom or an organic group. Further, -CH ₂ CH _{2- in} R ¹⁰¹ may be replaced with -CH = CH-, and further, when any of the following groups is not adjacent to each other,- It may be replaced with a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, where M ¹ is a hydrogen atom. Or represents a group represented by a methyl group.)
R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group.
R ³ represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-
R ^{4 to} R ⁷ are independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and haloalkoxy group having 1 to 6 carbon atoms. Represents a substituent selected from the group consisting of groups, cyano groups, and nitro groups.
In addition, R ² , R ³ and R ⁴ or R ² , R ³ and R ⁶ may be combined to form an aromatic group.
n is an integer from 0 to 3. )

As a fourth aspect, the cured film-forming composition according to any one of the first to third aspects, wherein the crosslinking agent of the component (B) is a crosslinking agent having a methylol group or an alkoxymethyl group.
As a fifth aspect, among the first to fourth aspects, which further contains a polymer having at least one group selected from the group consisting of (C) hydroxy group, carboxyl group, amide group, amino group, and alkoxysilyl group. The cured film forming composition according to any one item.
As a sixth aspect, the cured film-forming composition according to any one of the first to fifth aspects, which further contains (D) a crosslinking catalyst.
As a seventh aspect, (E) reacts with at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or the group A. The cured film-forming composition according to any one of the first to sixth aspects, which contains a compound having at least one group.
As the eighth aspect, the cured film formation according to any one of the first to seventh aspects containing 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A). Regarding the composition.
As the ninth viewpoint, the fifth to eighth viewpoints containing 1 part by mass to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the cross-linking agent of the component (A) and the component (B). The cured film forming composition according to any one item.
As a tenth viewpoint, the sixth to ninth viewpoints containing 0.01 part by mass to 20 parts by mass of the component (D) with respect to 100 parts by mass of the total amount of the cross-linking agent of the component (A) and the component (B). The cured film forming composition according to any one of the viewpoints.
As the eleventh viewpoint, the seventh to tenth viewpoints containing 1 part by mass to 100 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of the cross-linking agent of the component (A) and the component (B). The cured film forming composition according to any one item.

As a twelfth aspect, the present invention relates to a cured film obtained from the cured film forming composition according to any one of the first to eleventh viewpoints.

As a thirteenth viewpoint, the present invention relates to an alignment material obtained from the cured film forming composition according to any one of the first to eleventh viewpoints.

As a fourteenth aspect, the present invention relates to a retardation material, which is formed by using a cured film obtained from the cured film forming composition according to any one of the first to eleventh viewpoints.

According to the present invention, it is possible to provide a cured film showing good liquid crystal orientation and excellent adhesion to a liquid crystal layer, and a cured film forming composition suitable for forming the cured film. According to the present invention, it is possible to provide an alignment material having excellent liquid crystal orientation and light transmission. Further, according to the present invention, it is possible to provide a retardation material capable of high-precision optical patterning.

<Cured film forming composition>
The cured film-forming composition of the present invention contains (A) a reaction product of a polymer having an epoxy group and a cinnamic acid derivative having a group containing a polymerizable double bond, and (B) a cross-linking agent. The cured film-forming composition of the present invention is a group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group as the component (C) in addition to the above components (A) and (B). It can also contain a polymer having at least one group selected from. Furthermore, a cross-linking catalyst can also be contained as the component (D). Further, as the component (E), at least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least one group that reacts with the group A It can contain a compound having one group. Then, other additives can be contained as long as the effects of the present invention are not impaired.
The details of each component will be described below.

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

<Polymer with epoxy group>
The polymer having an epoxy group can be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.

Specific examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic. Acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylate-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxy Heptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like can be mentioned.

Other polymerizable unsaturated compounds include (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, methacrylate aryl esters, acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, and maleimides. Examples thereof include compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds.

Specific examples of these include alkyl methacrylate esters such as 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 acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; as methacrylate cyclic alkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8- Ilmethacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl methacrylate, isobolonyl methacrylate, cholestanyl methacrylate, etc .; as the acrylic acid cyclic alkyl ester, for example, cyclohexyl acrylate, 2-methylcyclohexyl Esters, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl acrylate, isobolonyl acrylate, choles Tanyl acrylate and the like; phenyl methacrylate, benzyl methacrylate and the like as methacrylic acid aryl esters; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Etc; Examples of bicyclounsaturated compounds include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2. 1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2] .2.1] Hept-2-ene, 5,6-diethoxybicyclo [2.2.1] Hept- 2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6- Di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5 -Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2] .1] Hept-2-ene and the like; examples of maleimide compounds include phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-. Maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acrydinyl) maleimide, etc .; as unsaturated aromatic compounds, for example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene , Vinyltoluene, p-methoxystyrene, etc .; as conjugated diene compounds, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.; as unsaturated monocarboxylic acids, for example, acrylic acid, methacrylic acid, etc. , Crotonic acid, etc .; as unsaturated dicarboxylic acids, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .; as unsaturated dicarboxylic acid anhydrides, each of the unsaturated dicarboxylic acid anhydrides; Examples of unsaturated compounds include acrylonitrile, maleimide, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate and the like.

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

The synthesis of the polymer having an epoxy group can be carried out by a known radical polymerization method preferably in a solvent in the presence of a suitable polymerization initiator.

As the polymer having an epoxy group, a commercially available product may be used. Examples of such commercially available products include EHPE3150, EHPE3150CE (above, manufactured by DIC CORPORATION (formerly DIC CORPORATION), UG-4010, UG-4035, UG-4040, UG-4070 (above, Toa Synthetic). ALUFON series manufactured by ALUFON series), ECN-1299 (manufactured by Asahi Kasei Co., Ltd.), DEN431, DEN438 (all manufactured by Dow Chemical Corporation), jER-152 (manufactured by Mitsubishi Chemical Corporation (formerly Japan Epoxy Resin Co., Ltd.)) , Epicron N-660, N-665, N-670, N-673, N-695, N-740, N-770, N-775 (above, DIC Corporation (formerly Dainippon Ink and Chemicals Co., Ltd.) ), EOCN-1020, EOCN-102S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.) and the like.

<Cinnamic acid derivative having a group containing a polymerizable double bond>
As the polymerizable double bond, a carbon-carbon double bond is preferable. Examples of the group containing a carbon-carbon double bond include a vinyl group, a (meth) acryloyl group, an acrylamide group and the like, and a (meth) acryloyl group is preferable.

式（１）中、Ａ^１とＡ^２はそれぞれ独立に、水素原子またはメチル基を表し、
Ｒ^１は下記式（ｃ−２）

（式（ｃ−２）中、破線は結合手を表し、Ｒ^１０１は炭素数１〜３０のアルキレン基を表し、このアルキレン基の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ^１０１中の−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−に置き換えられていてもよく、さらに、次に挙げるいずれかの基が互いに隣り合わない場合において、−Ｏ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、−ＮＨＣＯＮＨ−及び−ＣＯ−からなる群から選ばれる基に置き換えられていてもよく、Ｍ^１は水素原子又はメチル基を表す。）で表される基を表し、
Ｒ^２は２価の芳香族基、２価の脂環族基、２価の複素環式基または２価の縮合環式基を表し、
Ｒ^３は単結合、酸素原子、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨＣＯＯ−または−ＯＣＯＣＨ＝ＣＨ−を表し、
Ｒ^４〜Ｒ^７はそれぞれ独立に水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数１〜６のハロアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のハロアルコキシ基、シアノ基、及びニトロ基からなる群から選ばれる置換基を表し、
また、Ｒ^２、Ｒ^３及びＲ^４又はＲ^２、Ｒ^３及びＲ^６は一緒になって芳香族基を形成してもよく、
ｎは０〜３の整数である。）As the cinnamic acid derivative having a group containing a polymerizable double bond, a compound represented by the following formula (1) is preferable.

In formula (1), A ¹ and A ² independently represent a hydrogen atom or a methyl group, respectively.
R ¹ is the following formula (c-2)

(In the formula (c-2), the broken line represents a bond, R ¹⁰¹ represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group are replaced with a fluorine atom or an organic group. Further, -CH ₂ CH _{2- in} R ¹⁰¹ may be replaced with -CH = CH-, and further, when any of the following groups is not adjacent to each other,- It may be replaced with a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, where M ¹ is a hydrogen atom. Or represents a group represented by a methyl group.)
R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group.
R ³ represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-
R ^{4 to} R ⁷ are independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and haloalkoxy group having 1 to 6 carbon atoms. Represents a substituent selected from the group consisting of groups, cyano groups, and nitro groups.
In addition, R ² , R ³ and R ⁴ or R ² , R ³ and R ⁶ may be combined to form an aromatic group.
n is an integer from 0 to 3. )

Examples of the divalent aromatic group R ^2, for example, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3,5,6 Tetrafluoro-1,4-phenylene group and the like; as the divalent alicyclic group of R ² , 1,2-cyclopropylene group, 1,3-cyclobutylene group, 1,4-cyclohexylene group and the like are used. Examples of the divalent heterocyclic group of R ² include a 1,4-pyridylene group, a 2,5-pyridylene group, a 1,4-furanylene group, and the like; as a divalent fused cyclic group of R ^2. For example, 2,6-naphthylene groups and the like can be mentioned respectively. As R ² is 1,4-phenylene group is preferred.

（式中、Ｍ^１は水素原子又はメチル基であり、ｓ１はメチレン基の数を表し、２乃至９の自然数である。）Preferred examples of the compound represented by the above formula (1) include the following formulas M1-1 to M1-5.

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

The compound represented by the above formula (1) can be synthesized by appropriately combining conventional methods of organic chemistry.

<Reaction between a polymer having an epoxy group and a specific cinnamic acid derivative>
The reaction product of the polymer having an epoxy group and the specific cinnamic acid derivative contained in the liquid crystal alignment agent of the present invention is a polymer having an epoxy group as described above and the specific cinnamic acid derivative, preferably a catalyst. It can be synthesized in the presence, preferably by reacting in a suitable organic solvent.
The ratio of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 0.05 mol, based on 1 mol of the epoxy group contained in the polymer having an epoxy group. It is 1.3 mol, more preferably 0.1 to 1.1 mol.
As the organic catalyst that can be used here, a compound known as a so-called curing accelerator that promotes the reaction between an organic base or an epoxy compound and an acid anhydride can be used.

Examples of the organic base include 1-2 secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrol; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and the like. Tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide can be mentioned. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; and quaternary organic amines such as tetramethylammonium hydroxide. preferable.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine and triethanolamine; 2-methylimidazole and 2-n-heptylimidazole. , 2-n-Undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2- Ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1 -(2-Cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxymethyl) imidazole, 1- (2-) Cyanoethyl) -2-phenyl-4,5-di [(2'-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimerite, 1- (2-cyanoethyl) ) -2-phenylimidazolium trimerite, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1') )] Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1')] ethyl-s-triazine, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1') ')] Imidazole compounds such as the isocyanuric acid adduct of ethyl-s-triazine; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; benzyltriphenylphosphonium chloride, tetra-n- Butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltrife Nylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n- Tertiary phosphonium salts such as butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate; 1,8-diazabicyclo [5.4.0] undecene Diazabicycloalkenes such as -7 and its organic acid salts; organic metal compounds such as zinc octylate, tin octylate, aluminum acetylacetone complexes; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n -Quaternium ammonium salts such as butylammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and ferric chloride; additives such as dicyandiamide and amines with epoxy resins, etc. High melting point dispersion type latent curing accelerator such as amine addition type accelerator; Microcapsule type latent curing acceleration in which the surface of the curing accelerator such as imidazole compound, organic phosphorus compound and quaternary phosphonium salt is coated with a polymer Agents: Amine salt-type latent curing accelerators: Potential curing accelerators such as high-temperature dissociation-type thermal cationic polymerization-type latent curing accelerators such as Lewis acid salt and Brensteadated acid salt.
Of these, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.

The ratio of the catalyst used is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and further preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer having an epoxy group. Is.
Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds and the like. Of these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferable from the viewpoint 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, more preferably 5 to 50% by mass. Will be done.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.
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 for the preparation of the liquid crystal alignment agent, the polymer contained in the solution may be isolated and then used for the preparation of the liquid crystal alignment agent, or the isolated polymer may be purified. It may be used for preparing a liquid crystal aligning agent.

<Ingredient (B)>
The component (B) in the cured film forming composition of the present invention is a cross-linking agent.
The cross-linking agent as the component (B) is preferably a cross-linking agent having a group forming a cross-link with the thermally cross-linkable functional group of the component (A), for example, a methylol group or an alkoxymethyl group.
Examples of the compound having these groups include methylol compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine and alkoxymethylated melamine.

Specific examples of alkoxymethylated glycol uryl include 1,3,4,6-tetrax (methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174), methylated urea resin (Product name: UFR (registered trademark) 65), Butylated urea resin (Product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd. (former Dainippon Ink and Chemicals) Examples thereof include urea / formaldehyde-based resins manufactured by Kogyo Co., Ltd. (highly condensed type, trade name: Beccamin (registered trademark) J-300S, P-955, N) and the like.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. As commercial products, Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX- 4000, BX-37, BL-60, BX-55H) and the like.

Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine. Compounds (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) MW-30, MW-22, MW- 11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MX-45, MX-410) , MX-302) and the like.

Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 and the like, and commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (above, Nippon Cytec Industries Co., Ltd.). ) (Formerly manufactured by Mitsui Cytec Co., Ltd.) and the like.

Further, as a cross-linking agent for component (B), a hydroxymethyl group (that is, a methylol group) or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylate, N-ethoxymethylacrylamide, N-butoxymethylmethacrylate and the like. Polymers made using acrylamide compounds or methacrylic amide compounds substituted with are also available.

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

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

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

The method for obtaining the above-mentioned polymer is not particularly limited. As an example, an acrylic polymer having a specific functional group 1 is produced in advance by a polymerization method such as radical polymerization. Next, by reacting the specific functional group 1 with a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound), the polymer as the component (B) is polymerized with a C = C double bond. Sex groups can be introduced.

Here, the specific functional group 1 is a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having an active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types of functional groups selected from these. To tell.

In the above-mentioned reaction, the preferred combination of the specific functional group 1 and the functional group of the specific compound and participating in the reaction is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, and a phenolic hydroxy group and an epoxy group. , A carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride. Further, a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxy group and isocyanate ethyl methacrylate.

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

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

The content of the cross-linking agent of the component (B) in the cured film forming composition of the present invention is preferably 1 part by mass to 500 parts by mass based on 100 parts by mass of the polymer which is the component (A), and more preferably. It is 5 parts by mass to 400 parts by mass. When the content of the cross-linking agent is too small, the solvent resistance of the cured film obtained from the cured film-forming composition is lowered, and the liquid crystal orientation is lowered. On the other hand, if the content is excessive, the liquid crystal orientation and storage stability may decrease.

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

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

Preferred examples of the polymer as the component (C) include acrylic polymers, hydroxyalkylcyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

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

Examples of the monomer having the 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 hydroxy group, a monomer having a carboxyl group, and an amino group. Examples thereof include a monomer having an alkoxysilyl group and a monomer having a group represented by the above formula 2.

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

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

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

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

Examples of the above-mentioned monomer having an amino group in the side chain include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate.

Examples of the monomer having an alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxy. Examples thereof include silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyltriethoxysilane.

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

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

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

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

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

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

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

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

The method for obtaining the acrylic polymer as an example of the component (C) is not particularly limited, but for example, a monomer containing a monomer having a specific functional group 2, a monomer having no specific functional group 2 if desired, and a polymerization initiator. It is obtained by a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent in which the above is coexisted. At that time, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group 2, a monomer having no specific functional group 2 used as desired, a polymerization initiator and the like. Specific examples will be described in the [Solvent] section described later.

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

Further, the solution of the acrylic polymer, which is an example of the component (C) obtained by the above method, is put into diethyl ether or water under stirring to reprecipitate, and the generated precipitate is filtered and washed, and then the precipitate is filtered and washed. It can be dried at room temperature or heat-dried under normal pressure or reduced pressure to obtain a powder of an acrylic polymer as an example of the component (C). By the above operation, the polymerization initiator and the unreacted monomer coexisting with the acrylic polymer which is an example of the component (C) can be removed, and as a result, the acrylic polymer which is an example of the purified component (C) can be removed. Powder is obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

The acrylic polymer, which is a preferable example of the component (C), preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight average molecular weight is more than 200,000 and is excessive, the solubility in a solvent may be lowered and the handleability may be lowered, and if the weight average molecular weight is less than 3000 and too small, curing is insufficient at the time of thermosetting. In some cases, the solvent resistance may decrease. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard material. The same shall apply hereinafter in this specification.

Next, examples of the polyether polyol which is a preferable example of the component (C) include polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol and bisphenol A, triethylene glycol and sorbitol, and propylene oxide, polyethylene glycol and polypropylene glycol. Can be mentioned with the addition of. Specific examples of the polyether polyol include ADEKA's ADEKA polyether P series, G series, EDP series, BPX series, FC series, CM series, NOF's Uniox (registered trademark) HC-40, HC-60, ST- 30E, ST-40E, G-450, G-750, Unior® TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400 , Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.

As a polyester polyol which is a preferable example of the component (C), a polyvalent carboxylic acid such as adipic acid, sebacic acid and isophthalic acid is reacted with a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol and polypropylene glycol. Things can be mentioned. Specific examples of the polyester polyol include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, manufactured by DIC. 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, Polyesters made by Kuraray P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F −2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like can be mentioned.

Examples of the polycaprolactone polyol which is a preferable example of the component (C) include ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyols include DIC Polylite® OD-X-2155, OD-X-640, OD-X-2568, Daicel Praxel® 205, L205AL, 205U, 208, 210, Examples thereof include 212, L212AL, 220, 230, 240, 303, 305, 308, 312 and 320.

As a preferable example of the component (C), a polycarbonate polyol obtained by reacting a multivalent alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like can be mentioned. Specific examples of the polycarbonate polyol include Daicel's Praxel (registered trademark) CD205, CD205PL, CD210, CD220, and Kuraray's C-590, C-1050, C-2050, C-2090, and C-3090.

Examples of celluloses which are preferable examples of the component (C) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl alkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and cellulose and the like. For example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

Cyclodextrins which are preferable examples of the component (C) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl-γ. Methylated cyclodextrin such as -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, 2,3-dihydroxypropyl-β-cyclodextrin, 2, Examples thereof include hydroxyalkylcyclodextrins such as 3-dihydroxypropyl-γ-cyclodextrin.

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

上記式中、Ｒ^２１は水素原子または炭素原子数１〜４のアルキル基を表し、ｎは繰り返し単位の数を表す自然数である。From the viewpoint of storage stability, the melamine formaldehyde resin of the component (C) preferably has a methylol group formed during polycondensation of melamine and formaldehyde alkylated. Examples of the melamine formaldehyde resin of the component (C) include a resin having a unit structure represented by the following formula.

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

The method for obtaining the melamine formaldehyde resin of the component (C) is not particularly limited, but generally, melamine and formaldehyde are mixed, weakly alkalineized with sodium carbonate, ammonia, etc., and then heated at 60 ° C to 100 ° C. Is synthesized by. Further, the methylol group can be made into an alkoxy by reacting with an alcohol.

The melamine formaldehyde resin as the component (C) preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and even more preferably 350 to 3500. If the weight average molecular weight is more than 5000 and is excessive, the solubility in a solvent may be lowered and the handleability may be lowered, and if the weight average molecular weight is less than 250 and too small, curing is insufficient at the time of thermosetting. In some cases, the effect of improving solvent resistance does not appear sufficiently.

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

Examples of the phenol novolac resin which is a preferable example of the component (C) include a phenol-formaldehyde polycondensate.

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

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

The content of the cured film-forming composition of the present invention when the component (C) is contained is preferably 100 parts by mass with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the cross-linking agent of the component (B). It is 400 parts by mass or less, more preferably 10 parts by mass to 380 parts by mass, and further preferably 40 parts by mass to 360 parts by mass. When the content of the component (C) is excessive, the liquid crystal orientation tends to decrease.

<Ingredient (D)>
The cured film-forming composition of the present invention may further contain a cross-linking catalyst as a component (D) in addition to the components (A) and (B).
As the cross-linking catalyst as the component (D), for example, an acid or a thermoacid generator can be preferably used. This component (D) is effective in accelerating the thermosetting reaction of the cured film-forming composition of the present invention.
Specific examples of the component (D) include a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof as the acid. The thermal acid generator is not particularly limited as long as it is a compound that thermally decomposes to generate an acid during heat treatment, that is, a compound that thermally decomposes at a temperature of 80 ° C. to 250 ° C. to generate an acid. ..

Specific examples of the above acids include hydrochloric acid or a salt thereof; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphor. Sulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylensulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, Sulfonic acid group-containing compounds such as 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid or Examples thereof include hydrates and salts.

Examples of compounds that generate acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3. -Pholuenetris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p- Toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate , N-ethyl-p-toluenesulfoneamide, and compounds represented by the following formulas:

等が挙げられる。

And so on.

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

<Ingredient (E)>
In the present invention, as the component (E), one or more polymerizable groups and at least one group A or the group A selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. It can also contain a compound having at least one group that reacts. This acts as a component for improving the adhesiveness of the formed cured film (hereinafter, also referred to as an adhesion improving component).

When a cured film formed from the cured film-forming composition of the present embodiment containing the component (E) is used as the alignment material, the polymerizable liquid crystal is provided so as to improve the adhesion between the alignment material and the layer of the polymerizable liquid crystal. The polymerizable functional group and the cross-linking reaction site of the alignment material can be linked by a covalent bond. As a result, the retardation material of the present embodiment, which is formed by laminating a cured polymerizable liquid crystal on the alignment material of the present embodiment, can maintain strong adhesion even under high temperature and high quality conditions, and can be peeled off or the like. Can show high durability against.

As the component (E), a monomer and a polymer having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group are preferable.
Such (E) components include a compound having a hydroxy group and a (meth) acrylic group, a compound having an N-alkoxymethyl group and a (meth) acrylic group, and an N-alkoxymethyl group and a (meth) acrylic group. Examples thereof include polymers having. Specific examples are shown below.

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

As an example of the component (E), a compound having one acrylic group and one or more hydroxy groups can also be mentioned. Preferred examples of such a compound having one acrylic group and one or more hydroxy groups will be given. The compound of the component (E) is not limited to the following compound examples.

（上記式中、Ｒ^１１は水素原子またはメチル基を表し、ｍは１〜１０の整数を表す。）

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

In addition, examples of the compound of the component (E) include a compound having at least one polymerizable group containing a C = C double bond in one molecule and at least one N-alkoxymethyl group.

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

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

（式中、Ｒ^３１は水素原子又はメチル基を表し、Ｒ^３２は水素原子、若しくは直鎖又は分岐の炭素原子数１乃至１０のアルキル基を表す）The component (E) may have any of the above groups, but preferably, for example, a compound represented by the following formula (X1) can be mentioned.

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

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and 1-methyl-n. -Butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl- n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2 , 3-Dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl Group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl- n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl -N-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2- Ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl- n-Butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, 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-methy Examples thereof include ru-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like. ..

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

式中、Ｒ^５１は水素原子又はメチル基を表す。
Ｒ^５２は炭素原子数２乃至２０のアルキル基、炭素原子数５乃至６の１価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む１価の脂肪族基を表し、構造中にエーテル結合を含んでいてもよい。
Ｒ^５３は直鎖又は分枝鎖の炭素原子数２乃至２０のアルキレン基、炭素原子数５乃至６の２価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む２価の脂肪族基を表し、構造中にエーテル結合を含んでいてもよい。
Ｒ^５４は直鎖又は分枝鎖の炭素原子数１乃至２０の２価乃至９価の脂肪族基、炭素原子数５乃至６の２価乃至９価の脂肪族環基、若しくは炭素原子数５乃至６の脂肪族環を含む２価乃至９価の脂肪族基を表し、これらの基の一つのメチレン基または隣り合わない複数のメチレン基がエーテル結合に置き換わっていてもよい。
Ｚは＞ＮＣＯＯ−、または−ＯＣＯＮ＜（ここで「−」は結合手が１つであることを示す。また、「＞」「＜」は結合手が２つであることを示し、かつ、どちらか１つの結合手にアルコキシメチル基（即ち−ＯＲ５２基）が結合していることを示す。）を表す。
ｒは２以上９以下の自然数である。Another embodiment of the compound having a polymerizable group containing a C = C double bond and an N-alkoxymethyl group of the component (E) is preferably a compound represented by the following formula (X2), for example. ..

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alkyl group having 2 to 20 carbon atoms, a monovalent aliphatic ring group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms. An ether bond may be included in the structure.
R ⁵³ is a straight-chain or branched chain containing an alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. Represents an aliphatic group of, and may contain an ether bond in the structure.
R ⁵⁴ is a straight-chain or branched chain having a divalent to 9-valent aliphatic group having 1 to 20 carbon atoms, a divalent to 9-valent aliphatic ring group having 5 to 6 carbon atoms, or a carbon atom number of 5. It represents a divalent to 9-valent aliphatic group containing to 6 aliphatic rings, and one methylene group of these groups or a plurality of non-adjacent methylene groups may be replaced with an ether bond.
Z indicates> NCOO- or -OCON <(where "-" indicates that there is one bond, and ">" and "<" indicate that there are two bonds, and Indicates that an alkoxymethyl group (that is, -OR52 group) is bonded to either one of the bonds).
r is a natural number of 2 or more and 9 or less.

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

The alkyl group having 1 carbon atom is a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl. Group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1, 1,2-trimethyl-n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , N-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecil group, n-eicosyl group, cyclopentyl group, cyclohexyl group, one or more of them having up to 20 carbon atoms. Examples include a group bonded in a range and a group in which one methylene of these groups or a plurality of non-adjacent methylene groups are replaced with an ether bond.

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

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

Examples of r include natural numbers of 2 or more and 9 or less, and 2 to 6 are preferable.

The content of the component (E) in the cured film forming composition of the embodiment of the present invention is preferably 1 with respect to 100 parts by mass of the total amount of the polymer as the component (A) and the cross-linking agent of the component (B). It is by mass to 100 parts by mass, more preferably 5 parts by mass to 70 parts by mass. By setting the content of the component (E) to 1 part by mass or more, sufficient adhesion can be imparted to the formed cured film. However, when the amount is more than 100 parts by mass, the liquid crystal orientation tends to decrease.

Further, in the cured film forming composition of the present embodiment, the component (E) may be a mixture of a plurality of types of the compound of the component (E).

<Solvent>
The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at that time may be sufficient as long as it can dissolve the component (A), the component (B) and, if necessary, the component (C), the component (D), the component (E) and / or other additives described later. The type and structure are not particularly limited.

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

When a cured film is formed on a resin film to produce an alignment material using the cured film-forming composition of the present invention, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-butanol are used. , 2-Heptanone, isobutylmethyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate and the like are preferable from the viewpoint that the resin film exhibits resistance. ..

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

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

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

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

The blending ratio, preparation method, etc. when the cured film-forming composition of the present invention is used as a solution will be described in detail below.
The proportion of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 60% by mass, preferably 2. It is from mass% to 50% by mass, more preferably 2% by mass to 20% by mass. Here, the solid content refers to a composition obtained by removing the solvent from all the components of the cured film forming composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, for example, the component (B), the component (C), the component (D), the component (E) and the like are mixed in a solution of the component (A) dissolved in a solvent at a predetermined ratio to make it uniform. Examples thereof include a method of making a solution, or a method of further adding and mixing other additives as needed at an appropriate stage of this preparation method.

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

Further, it is preferable that the prepared solution of the cured film-forming composition is used after being filtered using a filter having a pore size of about 0.2 μm or the like.

<Hardened film, alignment material and retardation material>
The solution of the cured film-forming composition of the present invention is applied to a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, ITO. Substrates, etc.) and film substrates (eg, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) film, acrylic film, polyethylene. A coating film is formed by applying on a resin film such as a film) by bar coating, rotary coating, sink coating, roll coating, slit coating, rotary coating following the slit, inkjet coating, printing, etc., and then A cured film can be formed by heating and drying in a hot plate or an oven. The cured film can be applied as it is as an alignment material.

As a condition for heating and drying, the cross-linking reaction by the cross-linking agent may proceed to the extent that the components of the cured film (aligning material) do not elute into the polymerizable liquid crystal solution applied thereto. A heating temperature and heating time appropriately selected from the range of 200 ° C. and a time of 0.4 minutes to 60 minutes are adopted. The heating temperature and heating time are preferably 70 ° C. to 160 ° C., 0.5 minutes to 10 minutes.

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

Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, a retardation material such as a polymerizable liquid crystal solution having vertical orientation is applied onto the alignment material. , Can be oriented on the alignment material. Then, by curing the alignment material in the oriented state as it is, the retardation material can be formed as a layer having optical anisotropy. When the substrate on which the alignment material is formed is a film, it is useful as a retardation film.

Further, using two substrates having the alignment material of the present invention formed as described above, the alignment materials on both substrates are laminated so as to face each other via a spacer, and then between the substrates. It is also possible to inject a liquid crystal into a liquid crystal display element in which the liquid crystal is oriented.
As described above, the cured film forming composition of the present invention can be suitably used for manufacturing various retardation materials (phase difference films), liquid crystal display elements, and the like.

Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not construed as being limited thereto.

ＣＩＮ２：４−（３−メタクリルオキシプロピル−１−オキシ）桂皮酸

ＣＩＮ３：４−（６−アクリルオキシヘキシル−１−オキシ）桂皮酸

＜重合性基を有さない桂皮酸化合物＞
ＣＩＮ４：４−メトキシ桂皮酸

＜Ｂ成分＞
ＨＭＭ：下記の構造式で表されるメラミン架橋剤［サイメル（ＣＹＭＥＬ）（登録商標）３０３（三井サイテック（株）製）］

＜Ｄ成分＞
ＰＴＳＡ：ｐ−トルエンスルホン酸・一水和物
＜Ｅ成分＞
Ｅ−１：下記の構造式で示されるＮ−アルコキシメチル基およびアクリル基を有する化合物

＜溶剤＞
実施例及び比較例の各樹脂組成物は溶剤を含有し、その溶剤として、プロピレングリコールモノメチルエーテル（ＰＭ）を用いた。[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Raw materials>
GMA: Glycidyl methacrylate AIBN: α, α'-azobisisobutyronitrile BMAA: N-butoxymethylacrylamide MMA: Methyl methacrylate HEMA: 2-Hydroxyethyl methacrylate <Ceramic acid compound having a polymerizable group>
CIN1: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid

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

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

<Cinnamic acid compound having no polymerizable group>
CIN4: 4-Methoxycinnamic acid

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

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

<Solvent>
Each of the resin compositions 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 was as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd. And measured.
The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene-equivalent values.
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / Standard sample for preparing a calibration curve: Standard polystyrene manufactured by Showa Denko KK (molecular weight: about 197,000, 55, 100, 12,800, 3,950, 1,260,580).

<Synthesis of component A>
<Polymerization example 1>
An acrylic polymer solution was obtained by dissolving 15.0 g of GMA and 0.5 g of AIBN as a polymerization catalyst in 46.4 g of tetrahydrofuran and reacting them under heating and reflux for 20 hours. The obtained acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic polymer (P1) having an epoxy group. The obtained acrylic polymer had Mn of 25,000 and Mw of 10,000.

<Synthesis example 1>
PM 70 contains 5.2 g of the epoxy group-containing acrylic polymer (P1) obtained in Polymerization Example 1, 12.0 g of CIN1, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, and 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor. It was dissolved in 0.0 g and reacted at 100 ° C. for 20 hours. This solution was gradually added dropwise to 1000 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to give a polymer (PA-1). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

<Synthesis example 2>
PM 70 contains 5.2 g of the epoxy polymer (P1) having an epoxy group obtained in Polymerization Example 1, 11.0 g of CIN2, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, and 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor. It was dissolved in 0.0 g and reacted at 100 ° C. for 20 hours. This solution was gradually added dropwise to 1000 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to give a polymer (PA-2). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

<Synthesis example 3>
PM 70 contains 5.2 g of the epoxy group-containing acrylic polymer (P1) obtained in Polymerization Example 1, 12.0 g of CIN3, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst, and 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor. It was dissolved in 0.0 g and reacted at 100 ° C. for 20 hours. This solution was gradually added dropwise to 1000 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to give a polymer (PA-3). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

<Synthesis example 4>
Phenol novolac type epoxy resin N-775 (EPICLON series manufactured by DIC Corporation) 5.7 g, CIN1 11.0 g, ethyltriphenylphosphonium bromide 0.2 g as a reaction catalyst, and dibutylhydroxytoluene 0.2 g as a polymerization inhibitor. It was dissolved in 40.0 g of PM and reacted at 100 ° C. for 20 hours. This solution was gradually added dropwise to 500 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to give a polymer (PA-4). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

<Synthesis example 5>
The acrylic polymer (P1) having an epoxy group obtained in Polymerization Example 1 was 5.2 g, CIN1 10.0 g, CIN4 2.0 g, ethyltriphenylphosphonium bromide 0.1 g as a reaction catalyst, and dibutylhydroxytoluene 0 as a polymerization inhibitor. .2 g was dissolved in 70.0 g of PM and reacted at 100 ° C. for 20 hours. This solution was gradually added dropwise to 1000 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to give a polymer (PA-5). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

<Synthesis example 6>
5.2 g of the acrylic polymer (P1) having an epoxy group obtained in Polymerization Example 1, 6.5 g of CIN4, and 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst were dissolved in 48.0 g of PM, and the mixture was dissolved at 100 ° C. for 20 hours. It was reacted. This solution was gradually added dropwise to 500 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-6). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

<Synthesis example 7>
Feno-Lnovolac type epoxy resin N-775 (EPICLON series manufactured by DIC Corporation) 5.3 g, CIN4 5.0 g, and ethyltriphenylphosphonium bromide 0.2 g as a reaction catalyst were dissolved in PM 25.0 g and at 100 ° C. It was allowed to react for 20 hours. This solution was gradually added dropwise to 500 g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to give a polymer (PA-7). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

<Synthesis of component B>
<Polymerization example 2>
An acrylic polymer solution was obtained by dissolving 100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst in 193.5 g of PM and reacting at 90 ° C. for 20 hours. The obtained acrylic polymer had Mn of 2,700 and Mw of 3,900. The acrylic polymer solution was gradually added dropwise to 2000.0 g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PB-1).

<Synthesis of C component>
<Polymerization example 3>
An acrylic copolymer solution was obtained by dissolving 30.0 g of MMA, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst in 146.0 g of PM and reacting at 80 ° C. for 20 hours. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic copolymer (PC-1). The obtained acrylic copolymer had Mn of 18,000 and Mw of 32,800.

<Examples and comparative examples>
The cured film-forming compositions of Examples and Comparative Examples were prepared according to the compositions shown in Table 1. Next, a cured film was formed using each retardation material forming composition, and the orientation and adhesion of each of the obtained cured films were evaluated.

[Evaluation of orientation]
Each of the cured film-forming compositions of Examples and Comparative Examples was applied onto an ozone-treated COP film with a Wet film thickness of 4 μm using a bar coater. Each was heated and dried in a heat circulation type oven at a temperature of 110 ° C. for 60 seconds to form a cured film on the COP film. Each of the cured films was vertically irradiated with linearly polarized light of 313 nm at an exposure amount of 10 mJ / cm ² to form an alignment material. On the alignment material on the COP film, RMS03-013C, a polymerizable liquid crystal solution for horizontal alignment manufactured by Merck & Co., Inc., was applied using a bar coater at a Wet thickness of 6 μm. This coating film was exposed at 300 mJ / cm ² to prepare a retardation material. The retardation material on the produced substrate was sandwiched between a pair of polarizing plates, and the expression status of the phase difference characteristics in the retardation material was observed. Those in which the phase difference was exhibited without defects were marked with ○, and the phase difference was not exhibited. Those are described as x in the "Orientation" column. The evaluation results are summarized in Table 2 later.

[Evaluation of adhesion]
Each of the cured film-forming compositions of Examples and Comparative Examples was applied onto an ozone-treated COP film with a Wet film thickness of 4 μm using a bar coater. Each was heated and dried in a heat circulation type oven at a temperature of 110 ° C. for 60 seconds to form a cured film on the COP film. Each of the cured films was vertically irradiated with linearly polarized light of 313 nm at an exposure amount of 10 mJ / cm ² to form an alignment material. On the alignment material on the COP film, RMS03-013C, a polymerizable liquid crystal solution for horizontal alignment manufactured by Merck & Co., Inc., was applied using a bar coater at a Wet thickness of 6 μm. This coating film was exposed at 300 mJ / cm ² to prepare a retardation material. The retardation material was cut with a cutter knife so as to have 10 × 10 squares at intervals of 1 mm in length and width. A cellophane tape peeling test was performed on this notch using scotch tape. The evaluation result was "adhesion", and those in which all 100 squares were not peeled off were evaluated as ◯, and those in which even one square was peeled off were evaluated as x. The evaluation results are summarized in Table 2 later.

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

On the other hand, the alignment material obtained by using the cured film forming composition of Comparative Example showed good orientation, but could not obtain adhesion.

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

Claims (14)

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

In formula (1), A ¹ and A ² independently represent a hydrogen atom or a methyl group, respectively.
R ¹ is the following formula (c-2)

(In the formula (c-2), the broken line represents a bond, R ¹⁰¹ represents an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group are replaced with a fluorine atom or an organic group. Further, -CH ₂ CH _{2- in} R ¹⁰¹ may be replaced with -CH = CH-, and further, when any of the following groups is not adjacent to each other,- It may be replaced with a group selected from the group consisting of O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, where M ¹ is a hydrogen atom. Or represents a group represented by a methyl group.)
R ² represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group.
R ³ represents a single bond, an oxygen atom, -COO-, -OCO-, -CH = CHCOO- or -OCOCH = CH-
R ^{4 to} R ⁷ are independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and haloalkoxy group having 1 to 6 carbon atoms. Represents a substituent selected from the group consisting of groups, cyano groups, and nitro groups.
In addition, R ² , R ³ and R ⁴ or R ² , R ³ and R ⁶ may be combined to form an aromatic group.
n is an integer from 0 to 3. ) The cured film-forming composition according to any one of claims 1 to 3, wherein the cross-linking agent of the component (B) is a cross-linking agent having a methylol group or an alkoxymethyl group. (C) In any one of claims 1 to 4, further containing a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group. The cured film-forming composition according to the above. (D) The cured film-forming composition according to any one of claims 1 to 5, further comprising a cross-linking catalyst. (E) At least one group A selected from the group consisting of one or more polymerizable groups and a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, or at least one group that reacts with the group A. The cured film-forming composition according to any one of claims 1 to 6, which contains a compound having and. The cured film-forming composition according to any one of claims 1 to 7, which contains 1 part by mass to 500 parts by mass of the component (B) based on 100 parts by mass of the component (A). The item according to any one of claims 5 to 8, which contains 1 part by mass to 400 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the cross-linking agent of the component (A) and the component (B). The cured film forming composition according to the above. Any one of claims 6 to 9 containing 0.01 parts by mass to 20 parts by mass of the component (D) with respect to 100 parts by mass of the total amount of the cross-linking agent of the component (A) and the component (B). The cured film forming composition according to the item. The item according to any one of claims 7 to 10, which contains 1 part by mass to 100 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of the cross-linking agent of the component (A) and the component (B). The cured film forming composition according to the above. A cured film obtained from the cured film-forming composition according to any one of claims 1 to 11. An alignment material obtained from the cured film-forming composition according to any one of claims 1 to 11. A retardation material, which is formed by using a cured film obtained from the cured film forming composition according to any one of claims 1 to 11.