KR20140051074A - Optical alignment thermosetting composition, cured layer, color filter, liquid crystal display device, solid state imaging device, patterned retardation plate and optical device - Google Patents

Abstract

The present invention is to provide a material which has flatness properties, high solvent resistance, excellent photo-alignment properties, enough heat resistance, and high transparency after forming a cured layer and is soluble in glycol-based solvents, ketone-based solvents, or lactic acid ester-based solvents which are applicable in manufacturing overcoat of a color filter when forming the cured layer. The present invention relates to a polymer (A) having photo-alignment properties, thermosetting compositions comprising polyester amide acid and having alignment properties, and the uses thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermosetting composition having a photo-alignment property, a cured film, a color filter, a liquid crystal display device, a solid-state image pickup device, a patterned retardation plate and an optical device, PATTERNED RETARDATION PLATE AND OPTICAL DEVICE}

The present invention relates to a thermosetting composition having a photo-alignment property and a cured film formed therefrom. More specifically, the present invention relates to a thermosetting composition which is excellent in transparency, liquid crystal aligning ability, solvent resistance and heat resistance in a thermosetting film and the application of such a thermosetting film.

In the manufacturing process of an element such as a liquid crystal display element, various chemical treatments such as an organic solvent, an acid, and an alkali solution may be performed, or the surface may be locally heated to a high temperature when the wiring electrode is formed by sputtering. Thus, a surface protective film may be provided for the purpose of preventing deterioration, damage, deterioration, etc. of the surface of various devices. These protective films are required to have various properties capable of enduring various treatments in the manufacturing process as described above. Specifically, there is a need for a coating composition which does not cause deterioration such as chemical resistance such as heat resistance, solvent resistance, acid resistance and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, coating property, flatness, Light resistance and the like are required.

Particularly in recent years, high performance such as high viewing angle (high viewing angle), fast response, and high definition of a liquid crystal display device has been advanced, and when used as a color filter protective film, the transmittance of light transmitted through a color filter is maintained It is necessary to have a film having high transparency.

On the other hand, in recent years, introduction of a retardation material into a cell of a liquid crystal display has recently been studied at low cost, light weight, and the like. As such a retardation material, a material obtained by applying and orienting a polymerizable liquid crystal solution and then photo- . In order to orient such a retardation material, the lower layer film needs to be treated with a material having an orientation property after rubbing treatment or polarized UV irradiation. To this end, a phase difference material is formed after the liquid crystal alignment layer is formed on the overcoat of the color filter.

If a film serving as an overcoat of the liquid crystal alignment layer and the color filter can be formed, a reduction in cost and a reduction in the number of processes can be expected. Therefore, in recent years, a material that also serves as an overcoat for a liquid crystal alignment layer and a color filter has been actively studied.

In general, an acrylic resin having high transparency is used for overcoat of a color filter, and a method of increasing heat resistance and resistance of a solvent by thermosetting or photo-curing such an acrylic resin has been employed (Patent Document 1 and Patent Document 2).

On the other hand, a material comprising a solvent-soluble polyimide or polyamic acid is generally used for the liquid crystal alignment layer. It has been reported that these materials are completely imidized by post-baking and that sufficient resistance to solvent is imparted by the rubbing treatment (Patent Document 3).

However, the thermosetting or photo-curing acrylic resins described in Patent Document 1 and Patent Document 2 have appropriate transparency and solvent resistance, but even when subjected to rubbing treatment or polarized UV irradiation, the overcoat made of such acrylic resin does not exhibit sufficient orientation .

The liquid crystal alignment layer described in Patent Document 3 has a problem that transparency is low because it is used as an overcoat material of a color filter. In addition, since polyimide and polyamic acid have low solubility in glycol solvents, ester solvents and ketone solvents, it is difficult to apply them to an overcoat production line using such a solvent.

Prior art literature

[Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2000-103937

Patent Document 2: Japanese Patent Application Laid-Open No. 2001-194797

Patent Document 3: Japanese Patent Application Laid-Open No. 2005-037920

The present invention has been accomplished on the basis of the above-described circumstances, and an object of the present invention is to provide a cured film which has flatness, high solvent resistance, excellent optical alignment property to polymerizable liquid crystal, sufficient heat resistance and high transparency, And a material which can be dissolved in a glycol-based solvent, a ketone-based solvent or an estersester-type solvent which can be applied in the production of an overcoat of a color filter at the time of formation.

The inventors of the present invention conducted various studies to overcome the above-mentioned problems, and as a result, found that a photo-orientable thermosetting composition comprising a photo-orientable polymer and a polyester amide acid can solve the above problems and completed the present invention To the ship.

The present invention has the following configuration.

[1] A photo-alignment thermosetting composition comprising a polymer (A) having photo-alignment properties and a polyester amide acid (B).

[2] The polymer according to [1], wherein the polymer (A) having photo-alignment properties described in item [1] is a copolymer of a polymerizable monomer (a1) having a cyclic ether and a polymerizable monomer (a2) Wherein the thermosetting composition has an orientation property.

[3] The polymerizable monomer (a1) according to item [2], wherein the polymerizable monomer (a1) having a cyclic ether is at least one selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl (3-ethyl-3-oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, (2-ethyl-2-oxetanyl) methyl methacrylate. [2] The thermosetting composition having photo-alignment property according to [2].

[4] The polymerizable monomer (a2) according to item [2], wherein the polymerizable monomer (a2) having a photoadductivity described in the item [2] is a functional group of a structure in which the photoadductivity site is photodimerized (photo- dimerization) A thermosetting composition having photo-alignment properties.

[5] The thermosetting composition according to item [2], wherein the photo-alignable moiety of the photo-polymerizable monomer (a2) having photo-alignment properties is cinnamoyl.

[6] The polyester amide acid (B) as described in item [1], which is a polyester amide acid obtained by reacting tetracarboxylic acid dianhydride, diamine and polyhydric hydroxy compound as essential components [1 Wherein the thermosetting composition has photo-alignment property.

[7] A polyester amide obtained by reacting the polyester amide acid (B) described in item [1] with an essential component of tetracarboxylic acid dianhydride, diamine, polyhydric hydroxy compound and monovalent alcohol Acid content The thermosetting composition having photo-alignment properties according to [1].

[8] The optical alignment agent according to item [7], wherein the monovalent alcohol is isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl- Lt; / RTI >

[9] The polyester amide acid (B) according to item [1], wherein X is a tetra carboxylic acid dianhydride, Y is a diamine, and Z is a polyhydric hydroxy compound is represented by the following formula (1) Is obtained by reacting the thermosetting composition of the present invention in the same ratio as that of the thermosetting composition.

0.2? Z / Y? ... (One)

0.2? (Y + Z) /X? 1.5 ... ... (2)

[10] The thermosetting composition according to item [1], wherein the polyester amide acid (B) according to item [1] is a compound having a structural unit represented by the following formula (3) and formula (4).

(Wherein R ¹ is a tetracarboxylic acid dianhydride residue, R ² is a diamine residue, and R ³ is a polyhydric hydroxy compound residue).

[11] The method according to any one of [1] to [11], wherein the tetracarboxylic acid dianhydride is 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic dianhydride, 2,2- (3,4-dicarboxyphenyl)) hexafluoropropanic acid dianhydride and ethylene glycol bis (anhydrotrimellitate). [6] The thermosetting composition according to item [6], wherein the thermosetting composition is a thermosetting composition.

[12] The method according to any one of [1] to [12], wherein the diamine is at least one selected from the group consisting of 3,3'-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) The thermosetting composition having photo-alignment properties according to item [6], which is the above compound.

[13] The method according to any one of [1] to [13], wherein the polyhydric hydroxy compound is selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8- A thermosetting composition having photo-alignment properties according to item [6], which is at least one compound.

[14] The thermosetting composition according to item [1], wherein the polyester amide acid (B) described in item [1] has a weight average molecular weight of 1,000 to 500,000.

[15] The thermosetting composition according to item [1], wherein the polymer (A) having photo-alignment properties described in item [1] has a weight average molecular weight of 2,000 to 200,000.

[16] A cured film obtained by heating the thermosetting composition having photo-alignment property described in item [1].

[17] A color filter using the cured film according to item [16] as a protective film.

[18] A liquid crystal display element using the color filter according to item [17].

[19] A solid-state image pickup device using the color filter according to item [17].

[20] A patterned retarder formed from the thermosetting composition having photo-alignment property described in item [1].

[21] An optical device comprising a retarder obtained by using the thermosetting composition having photo-alignment property described in item [1].

The thermosetting composition having photo-alignment property of the present invention can form a cured film having a liquid crystal aligning ability (photo-alignment property) by light irradiation in addition to high transparency, high solvent resistance, high heat resistance and flatness, And as an overcoat forming material. In particular, it is possible to form a film having both the characteristics of both the liquid crystal alignment layer and the overcoat layer of the color filter at one time, thereby simplifying the manufacturing process and reducing the cost by reducing the number of processes.

The thermosetting composition having photo-alignment properties of the present invention is particularly suitable for patterned retardation plates used in three-dimensional (3D) displays, built-in retardation plates for liquid crystal monitors, and overcoats of color filters having a photo alignment function.

1. Thermosetting composition having photo-alignment property of the present invention

The present invention relates to a thermosetting composition having a photo-alignment property, which comprises a polymer (A) having photo-alignment properties and a polyester amide acid (B).

A preferable mixing ratio of the polymer (A) having a photo-alignment property and the polyester amide acid (B) is preferably in the range of from 10 to 100 parts by mass, based on the total amount of the polymer (A) and the polyester amide acid (B) The content of polymer (A) having photo-alignment property is usually 50% by weight to 95% by weight, more preferably 50% by weight to 90% by weight, and still more preferably 50% by weight to 85% by weight. The content of the polyester amide acid (B) is usually 5% by weight to 50% by weight based on the total amount of the polymer (A) having photo-alignment properties and the polyester amide acid (B) % To 50 wt%, and more preferably 15 wt% to 50 wt%.

1-1. The polymer (A) having photo-

The photo-aligned polymer (A) is a copolymer of a polymerizable monomer (a1) having a cyclic ether and a polymerizable monomer (a2) having a photo-alignment property. (Molar ratio) between the cyclic ether-containing polymerizable monomer (a1) and the photo-orientable polymerizable monomer (a2) is preferably from 1 mole of the polymerizable monomer (a1) having a cyclic ether to the cyclic ether- The polymerizable monomer (a2) having photo-alignment properties is 1 to 20 moles, more preferably 1 to 10 moles, and still more preferably 1 to 5 moles.

1-2. The polymerizable monomer (a1) having a cyclic ether

Examples of the polymerizable monomer (a1) having a cyclic ether include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, 2-oxetanyl) methyl methacrylate. Of these, glycidyl methacrylate is preferable. These polymerizable monomers having a cyclic ether are preferred from the viewpoints of heat resistance, chemical resistance and the like of the resulting thermosetting composition.

1-3. The polymerizable monomer (a2) having photo-

The photo-orientable region of the polymerizable monomer (a2) having photo-alignment property means a functional group having a structure in which light is irradiated to generate anisotropy by a reaction such as photodimerization, photoisomerization, photolysis, photo-crosslinking, etc. Among these, A functional group having a structure generating dimerization, photoisomerization and the like is preferable.

Examples of the functional group capable of generating light dimerization include, for example, a substance having a cinnamate skeleton [K. Ichimura et al., "Macromolecules" (30, 903 (1997)), substances with an azobenzene skeleton [K. 298, 221 (1997)), a substance having a hydrazano- [beta] -ketoester skeleton [S. Yamamura et al., "Liquid Crystals" (vol. 13, No. 2, page 189 (1993)), substances having a stilbene skeleton [J. Macromolecules "(20, 2241 (1987)) of G. Victor and J. M. Torkelson, and substances with spiropyran skeleton [K. A group derived from "Chemistry Letters" (page 1063 (1992) by Ichimura et al.) And "Thin Solid Films" (vol. 235, page 101 (1993) by K. Ichimura et al. Specific examples thereof include cinnamoyl, calcon, coumarin, and anthracene. Of these, cinnamoyls having high transparency and photo-dimerization reactivity in the visible light region are preferred.

Examples of the cinnamoyl group include groups having at least one of the structures represented by the following formulas (I-1) to (I-3).

In the above formulas, R ⁴ represents hydrogen, alkyl of 1 to 20 carbon atoms in which arbitrary hydrogen may be substituted by fluorine, preferably alkyl of 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted by fluorine, More preferably methyl. m represents an integer of 0 to 6, preferably 2, 4 or 6; In addition, one to four of any hydrogen in the phenylene contained in the above formulas may be substituted with fluorine, methyl or methoxy.

Among the groups represented by the above formulas (I-1) to (I-3), groups represented by the formula (I-3) are preferable.

The structural moiety causing photo-isomerization, which can be taken as the photo-orientable moiety of the polymerizable monomer (a2) having photo-alignment, refers to a moiety that changes to a cis body and a trans-isomer by light irradiation. Specific examples thereof include azobenzene structure, And a benz structure. Of these, the azobenzene structure is preferable in view of the height of the reactivity.

Examples of the polymerizable monomer (a2) having a photo-alignment property include monomers having the structural units represented by the following formulas (I-1-1), (I-2-1) or (I-3-1) .

In the above formulas, the parenthesized portion to which the suffix x is attached is included in the polymer main chain, and x represents the molar fraction (x < 1) of the constituent unit contained in the polymer having photo-orientation.

In the above formulas, R ⁴ represents hydrogen, alkyl of 1 to 20 carbon atoms in which arbitrary hydrogen may be substituted by fluorine, preferably alkyl of 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted by fluorine, More preferably methyl.

In the above formulas, R ⁵ represents hydrogen, alkyl of 1 to 20 carbon atoms in which arbitrary hydrogen may be substituted by fluorine, or alkoxy of 1 to 20 carbon atoms in which arbitrary hydrogen may be substituted by fluorine, Alkyl of 1 to 5 carbon atoms in which hydrogen of hydrogen may be substituted by fluorine, or alkoxy of 1 to 5 carbon atoms in which arbitrary hydrogen may be substituted by fluorine, and more preferably represents methyl or methoxy.

In the above formulas, R ⁶ represents hydrogen or methyl, preferably methyl.

In the above formulas, Z ¹ represents a single bond, -COO- or -OCO-, and preferably represents -COO-.

In the above formulas, o represents an integer of 2 to 6, preferably 2, 4 or 6, and p represents an integer of 0 to 2, preferably 0.

Any one to four hydrogen atoms of the phenylene contained in the above formulas may be substituted with fluorine, methyl or methoxy, but is preferably unsubstituted or methoxy substituted.

Examples of the photo-polymerizable monomer having a photo-alignment property to be the structural unit of the above formula (I-1-1) include the following formulas (I-1-1-a) to (I-1-1-1) (In the formulas, R ⁷ is hydrogen or methyl, and R ⁸ is alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 10 carbon atoms), and the like.

(I-2-1-a) to (I-2-1-l) shown below may be used as the polymerizable monomer having photo- the polymerizable monomer represented (in the formula, R ⁷ represents hydrogen or methyl, R ⁸ represents an alkyl group having 1 to 20 carbon atoms) and the like, the formula (I-a-2-1) Among these, .

(I-3-1-a) to (I-3-1-i) shown below may be used as the polymerizable monomer having photo- (In the following formulas, R ⁷ represents hydrogen or methyl, and R ⁸ represents alkyl having 1 to 20 carbon atoms), and the like.

Among these polymerizable monomers, the polymerizable monomer having an optical orientation which is the structural unit of the formula (I-3-1) are preferred, and expressed by the general formula (I-3-1), R ⁶ is methyl, o = 2, p = 0, and R ⁴ is a structural unit of methyl is more preferable.

1-4. Other polymerizable monomers

The polymer (A) having photo-alignment properties may contain other polymerizable monomer from the viewpoint of improving the photo-alignment property, adhesion property, and the like of the thermosetting composition having the photo-alignment property of the present invention. Specific examples of other polymerizable monomers include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride and carboxylic acid anhydride Radical polymerizable monomers such as styrene-based radical-polymerizable monomers such as styrene, methylstyrene, ethylstyrene, methoxystyrene, ethoxystyrene, acetoxystyrene, vinyltoluene, chloromethylstyrene and hydroxystyrene, Hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (Meth) acrylate radical polymerizable monomer such as tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, for example, a radically polymerizable monomer having a condensation ring such as tricyclo [5.2.1.0 ^2,6 ] decanyl N-substituted maleimide radical polymerizable monomers such as N-phenylmaleimide and N-cyclohexylmaleimide, for example, macromonomers of the above monomers such as polystyrene macromonomers and polymethylmethacrylate macromonomers, A radically polymerizable monomer having a heterocycle containing one or both of nitrogen and oxygen, such as propionyl, morpholine, and roile morpholine, a condensed-ring radically polymerizable monomer such as indene, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, p-styryltrimethoxy Silane radical polymerizable monomers such as silane, p-styryltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane, 4-hydroxyphenylvinylketone, 3-acetyl-4-hydroxyphenylvinylketone , But the present invention is not limited thereto.

The mixing ratio (molar ratio) of the respective monomers constituting the polymer (A) having photo-alignment property in the case of containing other polymerizable monomers is such that the polymerizable monomer (a1) having a photo- (A2) is 5 to 50 mol, preferably 10 to 45 mol, more preferably 15 to 40 mol, and the other polymerizable monomer is used in an amount of 5 to 40 mol, preferably 10 to 35 mol, Mol, and more preferably 15 to 30 mol.

The photo-aligned polymer (A) can be produced by, for example, polymerizing the polymerizable monomer (a1) having the cyclic ether, the polymerizable monomer (a2) having photo-orientation, and other monomers, Aliphatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane and cycloheptane such as methanol, ethanol, Propanol and the like, and ethers such as dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone and cyclopentanone, acetic acid esters such as ethyl acetate, butyl acetate and amyl acetate,? -Butyrolactone such as ethylene glycol, diethylene glycol, triethylene glycol Propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-methoxy-2-propanol and 3-methoxy-3-methyl- Alcohols and the like). These reaction solvents may be used singly or in combination of two or more.

(A1) having a cyclic ether and a polymerizable monomer (a2) having a photo-alignment property are reacted in the above solvents, and if necessary, the polymerizable monomer The polymerizable monomer (a1) having a cyclic ether, the polymerizable monomer (a2) having a photo-alignment property, and other monomers are reacted in the above solvents.

The weight average molecular weight of the obtained polymer (A) having optical alignment properties is usually 2,000 to 200,000, preferably 5,000 to 100,000. Within this range, the flatness of the thermosetting composition having the photo-alignment property of the present invention is improved.

1-5. The polyester amide acid (B)

The polyester amide acid (B) is obtained by reacting tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound as essential components. In order to synthesize the polyester amide acid (B), at least a solvent is required, and a liquid or gel-like thermosetting resin composition may be used in which the solvent is left as it is and the handling property is taken into consideration. May be used. The synthesis of the polyester amide acid may include a monohydric alcohol, a styrene-maleic anhydride copolymer and a silicone-containing monoamine as a raw material as necessary, and among these, monohydric alcohols from the viewpoint of molecular weight control desirable.

Further, the polyester amide acid (B) may contain a compound having a photo-orientable moiety and hydroxy in view of improvement of photo-orientation.

Examples of the polyester amide acid (B) include compounds having structural units represented by the following formulas (3) and (4).

(Wherein R ¹ is a tetracarboxylic acid dianhydride residue, R ² is a diamine residue, and R ³ is a polyhydric hydroxy compound residue).

1-6. Tetracarboxylic acid dianhydride

Examples of the tetracarboxylic acid dianhydride used in the present invention include organic acids having 2 to 30 carbon atoms. Specific examples thereof include 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2' 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylsulfone tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenylsulfone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride , 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4- Phenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate) (trade name: TMEG-100, available from Shin-Nihon Rika Co., Ltd. ) &Lt; / RTI &gt; Alicyclic tetracarboxylic acid dianhydrides such as carboxylic acid dianhydrides such as cyclobutanetetracarboxylic acid dianhydride, methylcyclobutane tetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, and cyclohexanetetracarboxylic acid dianhydride such as ethanetetra Aliphatic tetracarboxylic acid dianhydrides such as carboxylic acid dianhydride and 1,2,3,4-butanetetracarboxylic acid dianhydride (trade name: RIKACID BT-100, Shin-Nippon Rika Co., Ltd.).

Among them, an aromatic tetracarboxylic acid anhydride which gives a resin with good transparency is preferable, especially 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl (Trade name: TMEG-100, Shin-Nippon Rika Kagaku Co., Ltd. (trade name: TMEG-100, manufactured by Shin-Etsu Chemical Co., ) Is more preferable, and 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride are particularly preferable.

1-7. Diamine

Examples of the diamine used in the present invention include those having 2 to 30 carbon atoms, and specific examples thereof include 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4 ' (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [ Sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] Phenyl] sulfone, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane.

Of these, diaminodiphenylsulfones which give a resin with good transparency are preferable, particularly 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are more preferable , And 3,3'-diaminodiphenyl sulfone are particularly preferable.

1-8. Polyhydric hydroxy compound

Examples of the polyhydroxy compound used in the present invention include those having 2 to 20 carbon atoms, and specific examples thereof include polyethylene glycol having a molecular weight of 1,000 or less such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Examples thereof include polypropylene glycols having a molecular weight of 1,000 or less such as propylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, Diol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-heptanediol, , 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2-nonanediol, 1,9-nonanediol, 1,2-dodecanediol, 1,12-dodecanediol, and other diols such as 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,7- Triol, 1,2,8-octanetriol, 1, Trimethylol propane, pentaerythritol, dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name) Trade names), diethanolamine and triethanolamine.

Of these, preferred are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol having good solubility in a solvent , 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferred.

1-9. Monohydric alcohol

Specific examples of the monohydric alcohols used in the present invention include those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and specific examples thereof include methanol, ethanol, 1-propanol, isopropyl alcohol, And examples thereof include alcohols, benzyl alcohols, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzylcarbinol and 3-ethyl-3-hydroxymethyloxetane .

Of these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane are preferable. Benzyl alcohol is more preferable as the monohydric alcohol in consideration of the compatibility of the polyester amide acid formed by using them, the compatibility in the case of mixing the epoxy resin and the epoxy curing agent, and the coating property of the thermosetting composition as the final product on the color filter.

1-10. Solvent used in polymerization reaction

Specific examples of the solvent used in the polymerization reaction for obtaining the polyester amide acid (B) include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene Propyleneglycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-phyloridone and N, N-dimethylacetate Amides.

Of these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether are preferred.

These solvents may be used alone or in combination of two or more. If the amount of the solvent used is in the range of 30 wt% or less based on the total amount of the solvent, other solvent than the solvent may be mixed and used.

1-11. A compound having a photo-orientable portion and a hydroxy

The polyester amide acid (B) may contain a compound having a photo-orientable moiety and hydroxy, from the viewpoint of further improving the photo-alignment property of the photo-alignment thermosetting composition of the present invention. Specific examples of the compound having a photo-orientable portion and a hydroxy include methyl ester of 4- (8-hydroxyoctyloxy) cinnamate, methyl ester of 4- (6-hydroxyhexyloxy) cinnamate, 4- Hydroxyethyloxy) cinnamic acid methyl ester, 4- (3-hydroxypropyloxy) cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxy cinnamic acid methyl ester, (4-hydroxybutyloxy) cinnamic acid ethyl ester, 4- (4-hydroxybutyloxy) cinnamic acid ethyl ester, 4- (3-hydroxypropyloxy) cinnamic acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester, 4-hydroxyethyloxy cinnamic acid ethyl ester, Cinnamic acid ethyl ester , Phenyl ester of 4- (8-hydroxyoctyloxy) cinnamate, phenyl ester of 4- (6-hydroxyhexyloxy) cinnamate, phenyl ester of 4- (4-hydroxybutyloxy) cinnamate, 4- Hydroxypropyloxy) cinnamic acid phenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxy cinnamic acid phenyl ester, 4-hydroxy cinnamic acid phenyl ester, 4- (8- (4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4- (3-hydroxypropyloxy) cinnamic acid biphenyl ester, 4- , Biphenyl ester of 4- (2-hydroxyethyloxy) cinnamic acid, biphenyl ester of 4-hydroxymethyloxy cinnamate, biphenyl ester of 4-hydroxycinnamic acid, 8-hydroxyoctyl ester of cinnamic acid, 6-hydroxyhexyl cinnamate Ester, cinnamic acid 4-hydroxybutyl ester, Cinnamic acid esters such as cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester and cinnamic acid hydroxymethyl ester, such as 4- (8-hydroxyoctyloxy) azobenzene, 4- (4-hydroxybutyloxy) azobenzene, 4- (3-hydroxypropyloxy) azobenzene, 4- (2-hydroxyethyloxy) azobenzene, 4-hydroxymethyloxyazobenzene, 4 (4-hydroxybutyloxy) chalcone, 4- (4-hydroxybutyloxy) chalcone, 4- 4-hydroxymethyloxycalone, 4-hydroxycalcone, 4 '- (8-hydroxyoctyloxy) chalcone, 4- (2-hydroxyethyloxy) 4'- (6-hydroxyhexyloxy) chalcone, 4 '- (4-hydroxybutyloxy) chalcone, 4' - (3- hydroxypropyloxy) For example, 7- (8-hydroxyoctyloxy) coumarin, 7- (6-hydroxyhexyloxy) -cyclohexyloxycarbonyl, 7-hydroxymethyloxycoumarin, 7-hydroxymethyloxycoumarin, 7- (4-hydroxybutyloxy) coumarin, 7- 6-hydroxyhexyloxy coumarin, 6- (4-hydroxybutyloxy) coumarin, 6- (3-hydroxypropyloxy) coumarin, 6- Ethyloxy) coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxy coumarin, and the like, but are not limited thereto.

1-12. Process for producing polyester amide acid

In the process for producing a polyester amide acid used in the present invention, X mol of tetracarboxylic dianhydride, Y mol of diamine and Z mol of polyhydric hydroxy compound are reacted in the solvent. At this time, it is preferable that X, Y, and Z be determined in such a ratio that the relationship of the following formulas (1) and (2) is established between them. With such a range, the solubility of the polyester amide acid in the solvent is high, and thus the coating property of the composition is improved, and as a result, a cured film excellent in flatness can be obtained.

0.2? Z / Y? ... (One)

0.2? (Y + Z) /X? 1.5 ... ... (2)

The relationship of the above formula (1) is preferably 0.7? Z / Y? 7.0, and more preferably 1.3? Z / Y? 7.0. The relationship of the formula (2) is preferably 0.5? (Y + Z) / X? 0.9, more preferably 0.7? (Y + Z) / X? 0.8.

When the polyester amide acid used in the present invention has an acid anhydride group at the terminal of the molecule, the above-described monohydric alcohol may be added thereto if necessary. The polyester amide acid obtained by reacting by adding monohydric alcohol improves the compatibility with the epoxy resin and the epoxy curing agent and simultaneously improves the applicability of the thermosetting resin composition of the present invention containing them.

When the above-mentioned silicon-containing monoamine is reacted with a polyester amide acid having an acid anhydride group at the molecular end, the acid resistance of the obtained coating film is improved. Furthermore, monohydric alcohols and silicon-containing monoamines can be reacted simultaneously with polyester amide acids.

1-13. Silicon-containing monoamines

Specific examples of the silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4 -Aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p- Aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylmethyldiethoxysilane, and the like.

Of these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which are excellent in the acid resistance of the coating film, are preferable, and 3-aminopropyltriethoxysilane is particularly preferable.

The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of tetracarboxylic acid dianhydride, diamine and polyhydric hydroxy compound, because the reaction proceeds smoothly. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours. When the silicon-containing monoamine is reacted, after the reaction of the tetracarboxylic acid dianhydride and the diamine and the polyhydric hydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower, and then the silicon-containing monoamine is added thereto, For 0.1 to 6 hours. The monohydric alcohol may be added at any point in the reaction.

The order of addition of the reaction raw materials to the reaction system is not particularly limited. (2) adding tetracarboxylic acid dianhydride after dissolving the diamine and the polyhydric hydroxy compound in the reaction solvent, (3) adding tetracarboxylic dianhydride to the reaction solvent, (4) adding tetracarboxylic dianhydride, A tetracarboxylic dianhydride and a polyhydric hydroxy compound are preliminarily reacted and then a diamine is added to the reaction product, or (4) a tetracarboxylic dianhydride and a diamine are reacted in advance, and then a polyhydroxy compound is added to the reaction product. It can also be done as a method.

The polyester amide acid used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups. Specific examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. The molar ratio of styrene / maleic anhydride to styrene / maleic anhydride copolymer is 0.5 to 4, preferably 1 to 3, and more preferably 0.8 to 1.2.

Specific examples of the styrene-maleic anhydride copolymer include commercially available products such as SMA3000P, SMA2000P and SMA1000P manufactured by KAWAHARA PETROCHEMICAL CO., LTD. Of these, SMA1000P, which is excellent in heat resistance and scratch resistance, is particularly preferable.

The polyester amide acid synthesized as described above contains a constitutional unit represented by the above-mentioned formulas (3) and (4), and the terminal thereof is an acid anhydride derived from tetracarboxylic acid dianhydride, diamine or polyhydric hydroxy compound as a raw material Group, an amino group, or a hydroxy group, or an additive other than these compounds constitutes the terminal. In the above formulas (3) and (4), R ¹ is a tetracarboxylic acid dianhydride residue, preferably an organic group having 2 to 30 carbon atoms. R ² is a diamine residue, preferably an organic group having 2 to 30 carbon atoms. R ³ is a polyhydric hydroxy compound residue, preferably an organic group having 2 to 20 carbon atoms.

The weight average molecular weight of the obtained polyester amide acid is preferably 1,000 to 500,000, more preferably 2,000 to 200,000. Within this range, the flatness and heat resistance of the resulting cured film are improved.

1-14. Other ingredients

The thermosetting composition having photo-alignment property of the present invention may contain components other than those described above as needed within the scope of not impairing the object of the present invention. Examples of such other components include an epoxy curing agent, a coupling agent, a surfactant, an antioxidant, and a solvent.

1-14-1. Epoxy hardener

The thermosetting composition having photo-alignment properties of the present invention may contain an epoxy curing agent from the viewpoint of improving flatness, chemical resistance, and the like. As the epoxy curing agent, there are an acid anhydride curing agent, a polyamine curing agent, a polyphenolic curing agent, and a catalyst type curing agent, but an acid anhydride curing agent is preferable in coloring and heat resistance.

When an epoxy curing agent is added for the purpose of improving the flatness and chemical resistance, the ratio of the epoxy resin to the epoxy curing agent is 1 part by weight to 13 parts by weight of the epoxy curing agent relative to 100 parts by weight of the epoxy resin. Preferably 5 parts by weight to 13 parts by weight, and more preferably 8 parts by weight to 11 parts by weight. As to the addition amount of the epoxy curing agent, more specifically, it is preferable to add the carboxylic acid anhydride group or the carboxyl in the epoxy curing agent to the epoxy group so that the equivalent is 0.1 to 1.5 times. At this time, the carboxylic acid anhydride group is calculated by generating two carboxyl groups. The carboxylic acid anhydride group or the carboxyl group is added so as to have an equivalence ratio of 0.15 to 0.8, the flatness, chemical resistance and the like are further improved.

Specific examples of the acid anhydride-based curing agent include an aliphatic dicarboxylic acid anhydride, an aromatic polycarboxylic acid anhydride, and a styrene-maleic anhydride copolymer.

Specific examples of the aliphatic dicarboxylic acid anhydride include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and hexahydrotrimellitic anhydride. Specific examples of the aromatic polycarboxylic acid anhydrides include phthalic anhydride and trimellitic acid anhydride. Of these, trimellitic acid anhydride, hexahydrotrimellitic acid anhydride and the like are particularly preferable in balance of heat resistance and solubility in solvents.

1-14-2. Coupling agent

The thermosetting composition having photo-alignment property of the present invention may contain a coupling agent from the viewpoint of improving the adhesion with the substrate. The content of the coupling agent is preferably 1% by weight or more based on the total amount of the thermosetting composition from the viewpoint of improving heat resistance and solvent resistance, and more preferably 1% by weight to 20% by weight from the viewpoint of balance with other properties.

As the coupling agent, a silane-based, aluminum-based or titanate-based compound may be used. Specific examples thereof include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane (trade name: S510, Silane series, aluminum series such as acetalalkoxyaluminum diisopropylate, and titanate series such as tetraisopropyl bis (dioctylphosphite) titanate. Among them, the silane series is preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable because it has a large effect of improving the adhesion.

1-14-3. Surfactants

The thermosetting composition having the photo-alignment property of the present invention may contain a surfactant from the viewpoint of improving the wettability, leveling property or coatability to the base substrate. From this viewpoint, the content of the surfactant is preferably 0.005 wt% to 10 wt%, more preferably 0.01 wt% to 8 wt%, and even more preferably 0.01 wt% to 5 wt% with respect to the total amount of the thermosetting composition Do.

As such a surfactant, 45, Polypro KL-245, 75; 90; 95 (all trade names, products of KYOEISHA CHEMICAL CO., LTD.), Disperbyk 161, Disperbyk 162, Disperbyk 163, (All trade names, manufactured by Beck Chemie Japan (hereinafter referred to as &quot; Beck Chemie Japan &quot;), KP-365, KF-96-50CS and KF-50-100CS (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) (Commercially available from Shin-Etsu Chemicla Co., Ltd.), SURFORON SC-101, SURFRON KH-40 (all trade names, products of SEEMY Chemical Co.), Futargent 222F, FTX-218 (all trade names, manufactured by NEOS Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF- (Trade name, product of Mitsubishi Materials Corporation) (DENON) 1826M, PC-6862, PC-6862, Megafac F-477, Megafac F-477 7062C, and Erimina 208M (all of which are products of Marubishi oil chemical co. Ltd.), Fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkylpolyoxy (Fluoroalkylpolyoxyethylene ether), a fluoroalkyltrimethylammonium salt, a fluoroalkylaminosulfonate salt, a polyoxyalkylene sulfonate, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, Oxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene But are not limited to, stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, Phenyl ether disulfonic acid salt, and PC-7062C is preferable among them.

1-14-4. Antioxidant

The thermosetting composition having photo-alignment properties of the present invention may contain an antioxidant from the viewpoint of weatherability. From this viewpoint, the content of the antioxidant is preferably 0.01 wt% to 10 wt%, more preferably 0.05 wt% to 8 wt%, and even more preferably 0.1 wt% to 5 wt% with respect to the total amount of the thermosetting composition desirable. Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorous-based, and sulfur-based compounds. Among them, a hindered phenol-based antioxidant is more preferable.

Specific examples of the antioxidant include, for example, Irganox FF, Irganox 1035, Irganox 1035FF, Irganox 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irga ADK STAB AO-20, ADKSTAB AO-30, ADKSTAV AO-50, ADK STAB AO-50, And hindered phenols such as adecastab AO-60, adecastab AO-70 and adecastab AO-80 (all trade names, products of ADEKA). Of these, adecastab AO-60 is even more preferable in transparency, heat resistance, crack resistance and the like.

1-14-5. solvent

The thermosetting composition having photo-alignment properties of the present invention is mainly used in a solution state dissolved in a solvent. The solvent to be used at this time is not particularly limited so long as the components (A) and (B) and, if necessary, other additives can be dissolved.

Specific examples of the solvent include solvents such as methanol, ethanol, isopropanol, 1-propanol, butanol, 2-methyl-1-butanol, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate , Ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene Methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone,? -Butyrolactone, ethyl 2- Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3- Methyl ethyl ketone, ethyl methyl ketone, ethyl methyl ketone, methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

These solvents may be used singly or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate are more preferable because they can be applied in a production line for over-coloring a color filter and have good film-forming properties and high safety.

1-15. Preservation of thermosetting compositions having photo-alignment properties

When the thermosetting composition having photo-alignment properties of the present invention is stored at a temperature of -30 캜 to 25 캜, the stability of the composition over time is improved, which is preferable. When the storage temperature is from -20 占 폚 to 10 占 폚, precipitates are not present, and still more preferable.

1-16. Adjustment of coating liquid

The coating liquid may be adjusted by further diluting the thermosetting composition having the photo-alignment property of the present invention with the solvent according to the film thickness of the cured film to be formed.

2. The curing membrane of the present invention

The thermosetting composition having a photo-alignment property of the present invention may be prepared by mixing a photo-orientable polymer and a polyester amide acid, and adding a solvent, an epoxy curing agent, a coupling agent and a surfactant, depending on the desired properties, And uniformly mixing and dissolving them.

The thermosetting composition having photo-alignment properties prepared as described above (after being dissolved in a solvent in the case of a solid state without solvent) is coated on the surface of a substrate such as glass, PET (polyethylene terephthalate), or TAC (triacetylcellulose) For example, by removing the solvent by heating or the like, a coating film can be formed. The coating of the thermosetting resin composition on the surface of the substrate can be performed by a conventionally known method such as a spin coating method, a roll coating method, a dip coating method, and a slit coating method. Subsequently, such a coating film is heated (prebaked) in a hot plate or an oven. The heating conditions vary depending on the kind of each component and the mixing ratio, but it is usually 70 to 120 占 폚 for 5 to 15 minutes in an oven and 1 to 5 minutes in a hot plate. Thereafter, in order to cure the coating film, a cured film can be obtained by heat-treating the coating film at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, for 30 minutes to 90 minutes in the oven and for 5 minutes to 30 minutes in the hot plate.

The cured film thus obtained can be obtained by heating 1) the polyamic acid portion of the polyester amide acid is cyclodehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amide acid is optically oriented Molecular weight and 3) photo-orientable polymer are cured by polymerization with a cyclic ether of a polymer, and are thus high in molecular weight. Therefore, they are very rigid and excellent in transparency, heat resistance, solvent resistance, flatness, adhesion and resistance to sputtering. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be manufactured by using this color filter.

In addition to the protective film for the color filter, the cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film. Furthermore, the cured film of the present invention is also effective as a protective film of an LED light-emitting body.

In addition, an optical film can be obtained by using the liquid crystal alignment film obtained from the thermosetting composition having the photo-alignment property of the present invention. The optical film is suitable for a retardation plate such as an optical compensation film and a patterned retardation plate for realizing the improvement of the contrast of the liquid crystal display element and the expansion of the viewing angle range.

The optical film generally has a substrate, a liquid crystal alignment film, and an optically anisotropic layer. The optically anisotropic layer is formed by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound and various other components as required, onto the liquid crystal alignment film formed on a substrate, aligning molecules of the liquid crystal compound Followed by back polymerization. The optically anisotropic layer exhibits optical anisotropy expressed by the molecular orientation of the liquid crystalline compound. Accordingly, such an optical film can be suitably used, for example, as a patterned retardation plate. Such an optical film can be suitably used for various optical devices, for example, a liquid crystal display device.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Synthesis Example 1: Synthesis of Photoinduced Polymer (A1)

To a 500 ml four-necked flask equipped with a thermometer, a stirrer, a feed inlet, and a nitrogen gas inlet were added 2- {4- [(1E) -3-methoxy- 135.00 g of ethyl 2-methylprop-2-enoate, 15.00 g of glycidyl methacrylate, 15.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, 50.00 g of cyclopentanone was injected as a solvent, and polymerization was carried out by heating at a polymerization temperature of 90 캜 for 2 hours. The reaction solution was cooled to 30 캜 or lower to obtain a 25% by weight solution of polymer (A1) having photo-alignment property. The weight average molecular weight of the solution measured by GPC was 6,400 (in terms of polystyrene).

In the present invention, the weight average molecular weight was measured using a column oven CTD-20A, a detector RID-10A, a system controller CBM-20A, a pumping pump LC-20AD and an autosampler SIL-10AF (all trade names, Shimazu Seisakusho Co., Product) using a GPC system. Polystyrene calibration kit PL2010-0102 having a weight average molecular weight of 645 to 132,900 (for example, Varian Polymer Co., Ltd. PL2010-0102) and PLgel MIXED-D (Varian Polymer) were used as the standard polystyrene , And THF was used as a mobile phase (mobile phase) at a column temperature of 35 DEG C and a flow rate of 1 mL / min.

Synthesis Example 2: Synthesis of photo-orientable polymer (A2)

To a 500 ml four-necked flask equipped with a thermometer, a stirrer, a feed inlet, and a nitrogen gas inlet were added 2- {4- [(1E) -3-methoxy- 20.00 g of ethyl 2-methylprop-2-enoate, 30.00 g of glycidyl methacrylate, 15.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, 50.00 g of cyclopentanone as a solvent was introduced and heated at a polymerization temperature of 90 캜 for 2 hours to effect polymerization. The reaction solution was cooled to 30 캜 or lower to obtain a 25% by weight solution of polymer (A2) having photo-alignment property. The weight average molecular weight of this solution measured by GPC was 7,300 (in terms of polystyrene).

Synthesis Example 3: Synthesis of photo-orientable polymer (A3)

To a 500 ml four-necked flask equipped with a thermometer, a stirrer, a feed inlet, and a nitrogen gas inlet were added 2- {4- [(1E) -3-methoxy- 100.00 g of ethyl 2-methylprop-2-enoate, 20.00 g of glycidyl methacrylate, 40.00 g of 2-hydroxyethyl methacrylate, 40.00 g of 3-methacryloxypropyltrimethoxysilane, 20.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 66.60 g of cyclopentanone as a reaction solvent were charged and heated at a polymerization temperature of 90 ° C for 2 hours to effect polymerization. The reaction solution was cooled to 30 캜 or lower to obtain a 25% by weight solution of polymer (A2) having photo-alignment property. The weight average molecular weight of this solution measured by GPC was 8,100 (in terms of polystyrene).

Synthesis Example 4: Synthesis of polymer (A4) having orientation property

To a 500 ml four-necked flask equipped with a thermometer, a stirrer, a feed inlet, and a nitrogen gas inlet were added 2- {4- [(1E) -3-methoxy- 100.00 g of ethyl 2-methylprop-2-enoate, 20.00 g of glycidyl methacrylate, 80.00 g of 2-hydroxyethyl methacrylate, 2,2'-azobis (2, Dimethylvaleronitrile) and 66.60 g of cyclopentanone as a reaction solvent were charged, and polymerization was carried out by heating at a polymerization temperature of 90 ° C for 2 hours. The reaction solution was cooled to 30 캜 or lower to obtain a 25% by weight solution of polymer (A2) having photo-alignment property. The weight average molecular weight of the solution measured by GPC was 7,100 (in terms of polystyrene).

Synthesis Example 5: Synthesis of photo-orientable polymer (A5)

To a 500 ml four-necked flask equipped with a thermometer, a stirrer, a feed inlet, and a nitrogen gas inlet were added 2- {4- [(1E) -3-methoxy- 100.00 g of ethyl 2-methylprop-2-enoate, 20.00 g of glycidyl methacrylate, 80.00 g of 3-methacryloxypropyltrimethoxysilane as a polymerization initiator, 2,2'-azobis ( 2,4-dimethylvaleronitrile) and 66.60 g of cyclopentanone as a reaction solvent were charged and heated at a polymerization temperature of 90 ° C for 2 hours to effect polymerization. The reaction solution was cooled to 30 캜 or lower to obtain a 25% by weight solution of polymer (A2) having photo-alignment property. The weight average molecular weight of this solution measured by GPC was 6,800 (in terms of polystyrene).

Synthesis Example 6: Synthesis of polyester amide acid (B1)

To a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material feed inlet and a nitrogen gas inlet, 446.96 g of 3-methoxypropionate (hereinafter abbreviated as 'MMP') dehydrated and purified, 31.93 g of 1,4- 25.54 g of benzyl alcohol and 183.20 g of 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as'ODPA') were injected and stirred at 130 ° C for 3 hours in a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 占 폚, 29.33 g of 3,3'-diaminodiphenyl sulfone (hereinafter abbreviated as DDS) and 183.04 g of MMP were added and stirred at 20 to 30 ° C for 2 hours, The mixture was stirred at 115 캜 for 1 hour and cooled to 30 캜 or lower to obtain a 30% by weight solution of light yellow transparent polyester amide acid (B1). The weight average molecular weight of the solution measured by GPC was 4,200 (in terms of polystyrene).

Synthesis Example 7: Synthesis of polyester amide acid (B2)

504.00 g of dehydrated and purified propylene glycol monomethyl ether acetate (hereinafter abbreviated as 'PGMEA'), 47.68 g of ODPA, and 1000 g of SMA 1000P (trade name: PGMEA) were placed in a 1000 ml four-necked flask equipped with a thermometer, a stirrer, : 144.97 g of styrene-maleic anhydride copolymer, Kawahara Oil Co., Ltd.), 55.40 g of benzyl alcohol, 9.23 g of 1,4-butanediol, diethylene glycol methyl ethyl ether (hereinafter abbreviated as EDM) g were sequentially introduced, and the mixture was stirred at 130 캜 for 3 hours in a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 占 폚, 12.72 g of DDS and 29.68 g of EDM were added and stirred at 20 to 30 占 폚 for 2 hours and then stirred at 115 占 폚 for 1 hour and cooled to 30 占 폚 or lower to obtain pale yellow transparent A 30% by weight solution of the polyester amide acid (B2) was obtained. The weight average molecular weight of the solution measured by GPC was 21,000 (in terms of polystyrene).

Synthesis Example 8: Synthesis of polyester amide acid (B3)

To a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a feedstock inlet, and a nitrogen gas inlet, 446.96 g of MMP, 31.93 g of methyl ester of 4- (hydroxyethyloxy) cinnamate, 25.54 g of 1,4-butanediol, 183.20 g of ODPA And the mixture was stirred at 130 캜 for 3 hours under a dry nitrogen stream. Thereafter, the reaction solution was cooled to 25 占 폚, 29.33 g of DDS and 183.04 g of MMP were added and stirred at 20 占 폚 to 30 占 폚 for 2 hours and then stirred at 115 占 폚 for 1 hour and cooled to 30 占 폚 or lower, A 30 wt% solution of the transparent polyester amide acid (B3) was obtained. The weight average molecular weight of the solution measured by GPC was 3,200 (in terms of polystyrene).

Example 1: Preparation of thermosetting composition

A 25 wt% solution (hereinafter referred to as polymer A1) of the polymer A1 having photo-alignment property obtained in Synthesis Example 1, a 30 wt% solution of the polyester amide acid B1 obtained in Synthesis Example 3 (B1) (Product name: JNC), a surfactant PC-7062C (trade name: TMA), an epoxy curing agent (hereinafter referred to as TMA) Manufactured by Marubishi Yuka Kogyo Co., Ltd.), cyclopentanone as a solvent was mixed and dissolved in the weight of the following Table 1, and the mixture was filtered through a membrane filter (0.2 탆) to obtain a thermosetting composition. The composition of the obtained thermosetting composition is shown in Table 1.

[Table 1]

　

Examples 2 to 11 And Reference Example 1: Preparation of thermosetting composition

The thermosetting compositions of Examples 2 to 11 and Reference Example 1 were obtained by mixing and dissolving in the compositions shown in Table 2 as follows. And A1 to A5 are each a 25% by weight solution of polymers (A1) to (A5) having photo-alignment properties, and B1 to B3 each represent a polyester amide acid (B1) B3). &Lt; / RTI &gt;

[Table 2]

Comparative Example 1 and Comparative Example 2: Preparation of thermosetting composition

As in Examples 1 to 11, the components shown in Table 3 were mixed and dissolved to obtain the thermosetting compositions of Comparative Examples 1 and 2.

[Table 3]

Assessment Methods

1) Formation of cured film

The thermosetting composition was spin-coated on a glass substrate and a color filter substrate at an arbitrary number of revolutions of 400 rpm to 1,200 rpm for 10 seconds and prebaked on a hot plate at 80 캜 for 3 minutes to form a coating film. Thereafter, the coating film was cured by heating in an oven at 230 DEG C for 30 minutes to obtain a cured film having a film thickness of 0.5 mu m. The substrate taken out from the oven was returned to room temperature, and the film thickness of the obtained cured film was measured. For the measurement of the film thickness, a contact type film thickness measuring instrument P-15 manufactured by KLA-Tencor Japan Co., Ltd. was used, and the average value of the three measurements was taken as the film thickness of the cured film.

2) Flatness

The step on the surface of the cured film of the color filter substrate with the cured film obtained in the above 1) was measured using a contact type film thickness meter P-15 manufactured by KLA-Tencor Japan. The maximum value of the step (hereinafter abbreviated as the maximum step) between the R, G, and B pixels including the black matrix was defined as a numerical value of the flatness. The color filter substrate used was a pigment dispersed color filter (hereinafter abbreviated as CF) using a resin black matrix having a maximum step difference of about 1.1 mu m.

3) Transparency

TC-1800 manufactured by Tokyo Denshoku Co., Ltd. was used, and a glass substrate on which a cured film obtained in the above 1) was formed with reference to a glass substrate on which a cured film was not formed The light transmittance at a wavelength of 400 nm was measured. Good (G: Good) when the transmittance was 95 T% or more, and bad (NG: Good) when it was less than 95 T%.

4) Heat resistance

The substrate on which the cured film obtained in the above step 1) was formed was heated in an oven at 230 ° C for 1 hour to measure the light transmittance in the same manner as in 3), and then the film thickness was measured before and after heating Was calculated by the following equation.

(Film thickness after heating / film thickness before heating) x 100 (%)

(G: Good) when the change rate of the film thickness was less than -5% and a failure (NG: No Good) when the change rate of the film thickness after heating was -5% or more.

5) Solvent resistance

The substrate on which the cured film obtained in the above 1) was formed was immersed in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) at 25 ° C for 30 minutes to measure the change in film thickness. Before and after the immersion, the film thickness was measured in the same manner as in the above 1) and calculated by the following formula.

(Film thickness after immersion / film thickness before immersion) × 100 (%)

(G: Good) when the change rate of the film thickness is -5 to 5%, a defect (NG: No Good) when it exceeds 5% due to swelling or decreased by -5% Respectively.

6) Photo-orientation

Linearly polarized ultraviolet light having a wavelength of about 313 nm in a direction of 90 DEG relative to the coated surface was applied to the surface of the cured film obtained in the above step 1) at 500 mJ / Respectively. A phase difference material solution made of a liquid crystal monomer was coated on the substrate using a spin coater and then prebaked on a hot plate at 80 캜 for 1 minute to form a film having a film thickness of 0.5 탆. This substrate was exposed at an exposure amount of 1000 mJ / cm 2 in terms of 365 nm. It was judged that the alignment was good (G: Good) and the alignment was not bad (NG: No Good) in the case of orienting the polarized UV at an exposure amount of 500 mJ / cm 2 at 313 nm.

Table 4 shows the results obtained by the above-described evaluation methods for the thermosetting compositions of Examples 1 to 11 and Reference Example 1. [

[Table 4]

Table 5 shows the results obtained by the above-described evaluation methods for the thermosetting compositions of Comparative Examples 1 and 2.

[Table 5]

The thermosetting composition having photo-alignment properties according to the present invention is very useful as a material for liquid crystal alignment layers of optically anisotropic films or liquid crystal display devices and is also useful for various displays such as thin film transistor (TFT) type liquid crystal display devices and organic EL devices A retardation film, a patterned retardation film for 3D display, an interlayer insulating film of a TFT-type liquid crystal element, an overcoat of a color filter, an insulating film of an organic EL element, and the like .

Claims (21)

A thermosetting composition having photo-alignment properties comprising a polymer (A) having photo-alignment properties and a polyester amide acid (B). The photoelectric conversion device according to claim 1, wherein the photo-alignment polymer (A) according to claim 1 is a copolymer of a polymerizable monomer (a1) having a cyclic ether and a polymerizable monomer (a2) having photo- Wherein the thermosetting composition has an orientation property. The process according to claim 2, wherein the polymerizable monomer (a1) having a cyclic ether according to claim 2 is at least one compound selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, 3,4-epoxycyclo (3-ethyl-3-oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methyl acrylate, And (2-ethyl-2-oxetanyl) methyl methacrylate. 2. The thermosetting composition according to claim 1, wherein the thermosetting composition has a photo-alignment property. 3. The method of claim 2,
A thermosetting composition having a photo-alignment property, characterized in that the photo-orientable site of the polymerizable monomer (a2) having photo-alignment properties according to claim 2 is a functional group having a structure of photo-dimerization (photo-dimerization) or photo- . 3. The method of claim 2,
A thermosetting composition having photo-alignment property, wherein the photo-alignable moiety of the polymerizable monomer (a2) having photo-alignment properties according to claim 2 is cinnamoyl. The method according to claim 1,
A polyester amide acid according to claim 1, wherein the polyester amide acid (B) is a polyester amide acid obtained by reacting tetracarboxylic acid dianhydride, diamine and polyhydric hydroxy compound as essential components. / RTI &gt; The method according to claim 1,
Characterized in that the polyester amide acid (B) according to claim 1 is a polyester amide acid obtained by reacting tetracarboxylic acid dianhydride, diamine, polyhydric hydroxy compound and monovalent alcohol as essential components The thermosetting composition having photo-alignment property. The process according to claim 7, wherein the monohydric alcohol is isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether or 3-ethyl-3-hydroxymethyloxetane. Wherein the thermosetting composition has an orientation property. The method according to claim 1,
The polyester amide acid (B) according to claim 1, wherein X is a tetracarboxylic acid dianhydride, Y is a diamine and Z is a polyhydric hydroxy compound, and the relationship of the following formulas (1) and Wherein the thermosetting composition has a photo-alignment property.
0.2? Z / Y? (One)
0.2? (Y + Z) /X? 1.5 ... (2) The method according to claim 1,
A thermosetting composition having photo-alignment property, wherein the polyester amide acid (B) according to claim 1 is a compound having a constitutional unit represented by the following formula (3) and formula (4).

(Wherein R ¹ is a tetracarboxylic acid dianhydride residue, R ² is a diamine residue, and R ³ is a polyhydric hydroxy compound residue). The method according to claim 6,
Wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic dianhydride, 2,2- (bis , 4-dicarboxyphenyl)) hexafluoropropanic acid dianhydride and ethylene glycol bis (anhydrotrimellitate). The thermosetting composition according to claim 1, The method according to claim 6,
Wherein the diamine is at least one compound selected from 3,3'-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and bis (4- Wherein the thermosetting composition has photo-alignment properties. The method according to claim 6,
Wherein the polyhydric hydroxy compound is at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8- Wherein the thermosetting composition has the photo-alignment property. The method according to claim 1,
A thermosetting composition having photo-alignment property, wherein the polyester amide acid (B) according to claim 1 has a weight average molecular weight of 1,000 to 500,000. The method according to claim 1,
A thermosetting composition having photo-alignment property, wherein the photo-alignment polymer (A) according to claim 1 has a weight average molecular weight of 2,000 to 200,000. A cured film obtained by heating the thermosetting composition having a photo-alignment property according to claim 1. A color filter using the cured film according to claim 16 as a protective film. A liquid crystal display element using the color filter according to claim 17. A solid-state imaging device using the color filter according to claim 17. A patterned retardation plate formed from the thermosetting composition having a photo-alignment property according to claim 1. An optical device comprising a retarder obtained by using the thermosetting composition having photo-alignment property according to claim 1.