JP2000009914A - Thermosetting resin solution composition for color filter, color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin soln. compsn. which is suitable to prevent production of display failures in a liquid crystal display device and to prevent coating defects by incorporating a specified compd. and an epoxy compd. having specified groups in the side chains. SOLUTION: This thermosetting resin soln. compsn. for a color filter is obtd. by using a compd. having a carboxylic acid and at least one kind of alkoxysilane, silanol and silanol condensate in one molecule as a curing agent, and curing an epoxy compd. having 70 to 1000 mol.wt. and having a group of a planer structure in the side chains. The compd. as the curing agent is preferably a reaction product of an aminoalkoxysilane and an acid hydride. The group having a planer structure is preferably a fluorene group. The epoxy compd. preferably has a structure expressed by the formula, wherein R is -O- or -OCH2CH2O- and R' is hydrogen or <=4C alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin solution composition for a color filter, a color filter, and a liquid crystal display device, and more particularly to an overcoat for a color filter and the like in a liquid crystal display device. A thermosetting resin solution composition for a color filter, which has a high flattening property and provides a coating film having no optical anisotropy, and a color filter provided with the overcoat, The present invention relates to a liquid crystal display device using a color filter.

[0002]

2. Description of the Related Art In recent years, many color liquid crystal display devices in which a liquid crystal device is combined with a color filter for color separation have been proposed. Here, the color filter is composed of a large number of picture elements each including pixels of three primary colors, red, green and blue, formed on a light-transmitting substrate, and a display contrast is provided between each pixel. In order to increase the height, a light-shielding region (black matrix) having a certain width is provided, and some have an overcoat or a transparent electrode as necessary. The overcoat has the ability to flatten the surface of the color filter (flattening characteristics), the light-transmitting substrate that forms the lower layer, the adhesion to the pixel and the black matrix, and the adhesion to the transparent electrode that forms the upper layer, etc. Properties, adhesiveness with a sealant for constituting a liquid crystal cell, blocking properties of pixel impurity components, smoothness, light resistance, moisture and heat resistance, solvent resistance, chemical resistance, heat resistance, and manufacturing of liquid crystal cells A wide range of characteristics such as pressure resistance and toughness in the substrate bonding process at the time are required.

In particular, when a liquid crystal display device is required to have high performance such as a wide viewing angle and a high response speed, the flatness of a color filter is important, and the flattening characteristics of an overcoat are improved. Is desired. Further, in the case where a high viewing angle is required in the liquid crystal display device, it is desired that the overcoat has no optical anisotropy.

As such an overcoat, conventionally,
Thermosetting resin solution compositions for color filters, such as siloxane polymers, silicone polyimides, epoxy resins, and acrylic resins, have been used.

[0005]

However, the conventional thermosetting resin solution composition for a color filter has insufficient flattening characteristics, and in a liquid crystal display device, display defects due to surface irregularities of the color filter may be insufficient. Occurred in some cases. In addition, in a thermosetting resin solution composition for a color filter using an epoxy resin or the like, an optical anisotropy occurs in the overcoat, and in a liquid crystal display device, the display angle dependence is different between the left and right sides of the display device. In some cases, defects occurred.

Further, when the components of the thermosetting resin solution composition for a color filter have a low molecular weight or the reactivity of the components is low, the thermosetting resin solution is applied to a substrate to form an overcoat. By heating when forming a coat,
In some cases, the components evaporate and sublimate, resulting in coating defects.

The present invention remedies the disadvantages of the prior art,
A thermosetting resin solution composition for a color filter suitable for preventing the occurrence of display defects of a liquid crystal display device and the occurrence of coating defects, and a color filter using the thermosetting resin solution composition for a color filter, and a liquid crystal It is an object to provide a display device.

[0008]

In order to achieve the above object, the present invention has the following arrangement.

The thermosetting resin solution composition for a color filter according to the present invention comprises a compound having at least one of alkoxysilane, silanol, and silanol condensate and a carboxylic acid in the same molecule, and having a molecular weight of 70 to 70. An epoxy compound having a group having a planar structure in the range of 1,000 in a side chain.

The color filter of the present invention has an overcoat formed from the thermosetting resin solution composition for a color filter of the present invention.

Further, the liquid crystal display device of the present invention is characterized by using the color filter of the present invention, and is characterized in that the liquid crystal is driven by a thin film transistor.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have found that the following measures are effective for the above-mentioned problems (lack of flattening characteristics, optical anisotropy, sublimation / evaporation of constituent components) regarding the overcoat. I found something.

That is, in order to improve the flattening characteristics of the overcoat, the components of the thermosetting resin solution composition for color filters are reduced in molecular weight;
It is effective to reduce the shrinkage of the coating film in the curing reaction, and in order to reduce the optical anisotropy of the overcoat coating film, it is effective to prevent in-plane orientation of the coating film. In addition, it has been found that in order to prevent sublimation and evaporation of the thermosetting resin solution composition for a color filter, it is effective to optimize the molecular weight of the constituent components.

The authors of the present invention provide at least one of an alkoxysilane, a silanol, and a silanol condensate,
A thermosetting resin solution composition for a color filter which uses a compound having a carboxylic acid in the same molecule as a curing agent and cures an epoxy compound having a group having a planar structure having a molecular weight in the range of 70 to 1000 in a side chain. The present inventors have found that an excellent overcoat that achieves all of the above measures can be obtained by the physical system, and have reached the present invention.

The thermosetting resin solution composition for a color filter of the present invention has a small shrinkage at the time of curing and is excellent in flattening characteristics because the curing proceeds by a reaction between a carboxylic acid and an epoxy group.

Also, a compound having at least one of alkoxysilane, silanol, and silanol condensate and a carboxylic acid in the same molecule may have poor flattening characteristics if the molecular weight is too high. If the molecular weight is too low, sublimation and evaporation during heating are likely to occur.
00, more preferably 300 to 500.

By using a compound having such a molecular weight range, it is possible to obtain a thermosetting resin solution composition for a color filter having good flattening characteristics and no sublimation or evaporation during heating. Becomes

The method for obtaining a compound having at least one of alkoxysilane, silanol, and silanol condensate and a carboxylic acid in the same molecule is not particularly limited, and a compound having an alkoxysilane and a carboxylic acid may be used. It can be obtained by the reaction or polymerization of the compound, but is preferably obtained by the reaction between an aminoalkoxysilane and an acid anhydride because of easy availability of the compound and easy control of the molecular weight. In particular, the versatility of the material,
Considering the molecular weight, as aminoalkoxysilane, γ
-Aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltri Methoxysilane, N-β
(Aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like can be used.

The acid anhydride is not particularly limited as long as it is an acid anhydride having a carboxylic acid, but trimellitic anhydride is preferably used in view of availability and cost. In addition, when trimellitic acid and aminoalkoxysilane are reacted at an equimolar ratio, no acid anhydride remains, so that storage stability when mixed with an epoxy compound is improved. That is, as an acid anhydride,
When an acid dianhydride such as pyromellitic dianhydride is used, the acid anhydride remains when reacted with an aminoalkoxysilane in an equimolar ratio, but the reaction between the acid anhydride and the epoxy is fast. Therefore, storage stability becomes poor, which is not preferable.

The above aminoalkoxysilane is
It can be used in the state of being reacted with the acid anhydride, but it can also be used in the state of hydrolyzed silanol or in the state of hydrolyzed and condensed silanol. The hydrolysis is performed by adding water to the reaction product of the aminoalkoxysilane and the acid anhydride and reacting at a low temperature.The hydrolysis condensation is performed by adding water to the reaction product of the aminoalkoxysilane and the acid anhydride and heating the mixture. This is performed by distilling off water and alcohol. Here, an acid catalyst may be added to the hydrolysis and the hydrolysis and condensation.

In the thermosetting resin solution composition for a color filter of the present invention, the epoxy compound has a molecular weight of 70.
Since the side chain has a group having a planar structure in the range of １０００1000, it is possible to suppress the orientation of the cured polymer in the coating film surface. The side chain referred to here is a portion that protrudes from the main chain direction generated by the reaction between the epoxy group and the carboxylic acid. Here, a molecular weight of 70 to 10
When the molecular weight of the group having a planar structure in the range of 00 is smaller than 70, the effect of suppressing the orientation is reduced, and when it is larger than 1000, the reactivity with the curing agent is reduced. Therefore, it is preferably in the range of 70 to 1,000. The group having a planar structure is not particularly limited, and a benzene ring, a polycyclic aromatic, or the like can be used.

However, in view of the size of the planar structure, it is preferable to use fluorene as the group having a planar structure having a molecular weight in the range of 70 to 1,000.

Further, from the viewpoint of availability, it is more preferable to use an epoxy compound represented by the following general formula (1).

[0024]

Embedded image (Wherein, R _{is, -O -, - OCH 2 CH} 2 O- are shown,
R ′ represents hydrogen or an alkyl group having 4 or less carbon atoms. In the epoxy compound containing a fluorene group, the effect of suppressing sublimation and evaporation during heating can be obtained due to the presence of the fluorene group.

In the thermosetting resin solution composition for a color filter of the present invention, alkoxysilane, silanol,
A compound having at least one silanol condensate and a carboxylic acid in the same molecule; and a compound having a molecular weight of 70 to 100.
The mixing ratio of the epoxy compound containing a group having a plane structure in the range of 0 is 100 parts by weight of a compound having at least one of alkoxysilane, silanol, and silanol condensate and a carboxylic acid in the same molecule. On the other hand, the epoxy compound is 5 to 300 parts by weight, preferably 10 to 300 parts by weight.
250 parts by weight, more preferably 20 to 200 parts by weight. When the amount of the compound having at least one of alkoxysilane, silanol, and silanol condensate and the carboxylic acid in the same molecule is too small, the curing of the epoxy compound becomes insufficient. It is not preferable because the property is lowered.

A curing catalyst may be added to the thermosetting resin solution composition for a color filter of the present invention. Examples of the curing catalyst include, but are not limited to, amines, imidazoles, metal chelates and the like.

Solvents used in the thermosetting resin solution composition for color filters of the present invention include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and the like. Ethers such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Ethyl acetate, n-butyl acetate, 3-methoxy-3-methylbutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol Esters such as monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone,
Examples include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone. Among these, it is necessary to select a solvent in consideration of the applicability, the solubility of the constituent components, and the like, and they can be used alone or as a mixture of two or more. Moreover, about the solid content concentration of the thermosetting resin composition of this invention, 10-70%, Preferably it is 15-6 from a coating method and a viewpoint of solubility.
0%, more preferably 20 to 50%.

Further, a surfactant can be added to the thermosetting resin solution composition for a color filter of the present invention for the purpose of improving applicability and drying property. The amount of the surfactant is usually 0.01 to 10 parts by weight, preferably 0.03 to 1 part by weight, per 100 parts by weight of the resin.
Parts by weight. If the added amount is too small, there is no effect of improving the coating properties and drying properties. If the added amount is too large, on the contrary, poor coating properties and reduced toughness of the coating film are caused.

Specific examples of the surfactant include silicone oils such as dimethyl silicone oil and methyl phenyl silicone oil, alkyl, fluorine-modified silicone oil, polyether, alcohol-modified silicone oil, amino-modified silicone oil, and epoxy-modified silicone oil. Modified silicone oils such as phenol, carboxy, mercapto-modified silicone oils, anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as lauryl trimethyl ammonium chloride, lauryl dimethyl Amphoteric surfactants such as amine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauri Ether, polyoxyethylene stearyl ether, nonionic surfactant, such as sorbitan monostearate, and the like acrylic polymer.
In the present invention, the surfactant is not limited thereto, and one of the above surfactants may be used alone, or two or more of them may be used in combination.

As a method for applying the thermosetting resin solution composition for a color filter of the present invention on a substrate, the substrate is applied by a spin coater, a bar coater, a blade coater, a roll coater, a die coater, a screen printing method or the like. Various methods such as a method, a method of immersing a substrate in a solution, and a method of spraying a solution on a substrate can be used.

The color filter of the present invention is characterized by having an overcoat made of the thermosetting resin solution of the present invention.

The color filter according to the present invention comprises a black matrix formed on a light-transmitting substrate, a colored layer composed of three primary colors, and an overcoat, or a color filter formed on a light-transmitting substrate. Black matrix, three primary color layers, part of the three primary color layers on the black matrix, or a plurality of dot spacers formed by lamination of all layers, and an overcoat By using the thermosetting resin solution composition for a color filter of the present invention as an overcoat, the overcoat having good flatness and no optical anisotropy was sublimated and evaporated. It can be obtained without any coating defects due to objects and the like.

Here, the dot-shaped spacer makes it unnecessary to disperse the spacer in the liquid crystal display device manufacturing process, and greatly contributes to the improvement of the yield.

In the color filter of the present invention, a transparent electrode may be provided on the overcoat.

The components of the color filter of the present invention will be described.

First, a glass substrate is usually used as the light transmitting substrate.

Next, the black matrix is a light-shielding region between pixels and plays a role of improving the contrast of the liquid crystal display device. The black matrix is often formed of a metal thin film having a fine pattern. Cr,
Ni, Al, etc. are used. As a method for forming a metal thin film, a sputtering method, a vacuum evaporation method, and the like are widely used. Also, for fine patterns,
After a photoresist pattern is formed by photolithography, the metal thin film is etched using the resist pattern as an etching mask.

However, a black matrix formed of a metal thin film has a high manufacturing cost and causes an increase in the price of the color filter itself. Furthermore, Cr, which is generally used as a metal thin film for a black matrix, has a high reflectivity, and therefore has a problem that display quality is significantly reduced in places where external light is strong due to reflected light of Cr. Further, in order to reduce the reflectance of the black matrix, a method of providing a chromium oxide layer between Cr and the light-transmitting substrate has been proposed, but it is not preferable in terms of manufacturing cost.

Therefore, as a black matrix,
It is preferable to use a resin black matrix in which a light shielding agent is dispersed in a resin.

The light-shielding agent used in the resin black matrix includes carbon black, metal oxide powder such as titanium oxide and iron tetroxide, metal sulfide powder, and metal powder, as well as red, blue, and green. And the like. Among them, carbon black is particularly preferable because of its excellent light-shielding properties.

When carbon black is used as a light-shielding agent, it is preferable to mix a pigment of a complementary color to carbon black in order to make the color tone achromatic. As pigments for complementary colors, blue pigments and purple pigments can be used alone or as a mixture of both.

When carbon black and a pigment of a color complementary to carbon black are used as the light-shielding agent, the ratio of carbon black contained in the light-shielding agent should be 50% by weight or more in order to obtain high light-shielding properties. It is preferably 60% by weight or more, and more preferably 70% by weight or more.

Examples of typical pigments used as complementary colors of carbon black are shown by color index numbers.
Examples of blue pigments include Pigment Blue 15, 15:
1, 15: 2, 15: 3, 15: 4, 15: 6, 16,
21, 22, 60, 64, etc., with Pigment Blue 15, 15: 1, 15: 2, 15: 6 being particularly preferred. Examples of purple pigments include Pigment Violet 19, 23, 29, 31, 32, 33, 36, 3
7, 39, 43, 50, etc., and particularly, Pigment Violet 23, 31, 33, 43, 50 is preferable.

In addition, green pigments, yellow pigments, orange pigments, and the like may be added as appropriate, but the proportion incorporated in the light-shielding agent is preferably 10% by weight or less. If it is more than this, the light-shielding property per film thickness of the black matrix decreases, which is not preferable.

As the resin used for the resin black matrix, a transparent resin such as an acrylic resin or an epoxy resin can be used. However, in view of the heat resistance, light resistance and solvent resistance of the coating film, the resin is as follows. Preferably, a polyamic acid is used.

The polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine.

In the synthesis of polyamic acid, for example, aliphatic or alicyclic tetracarboxylic dianhydrides can be used, and specific examples thereof include:
1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a, 4,4
5,9b-Hexahydro-5- (tetrahydro-2,5
-Dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione; In addition, when an aromatic compound is used, a polyamic acid that can be converted into a film having good heat resistance can be obtained, and specific examples thereof include 3,3 ′, 4,4′-benzophenonetetracarboxylic acid. Dianhydride, pyromellitic dianhydride, 3,4,9,
10-perylenetetracarboxylic dianhydride, 3,3 ′,
4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride, 1,
2,5,6-naphthalenetetracarboxylic dianhydride,
3,3 ", 4,4" -paraterphenyltetracarboxylic dianhydride and 3,3 ", 4,4" -methterphenyltetracarboxylic dianhydride are exemplified. In addition, when a fluorine-based material is used, a polyamic acid that can be converted into a film having good transparency in a short wavelength region can be obtained, and specific examples thereof include 4,4 ′-(hexafluoroisopropylidene). ) Diphthalic anhydride; The present invention is not limited to these, and one or more tetracarboxylic dianhydrides are used.

As the diamine, for example, an aliphatic or alicyclic diamine can be used. Specific examples thereof include 1,3-diaminocyclohexane,
4-diaminocyclohexane, 4,4'-diamino-
3,3′-dimethyldicyclohexylmethane, 4,4 ′
-Diamino-3,3'-dimethyldicyclohexyl and the like. When an aromatic compound is used, a polyamic acid which can be converted into a film having excellent heat resistance can be obtained. Specific examples thereof include 4,4′-diaminodiphenyl ether and 3,4′-diamino. Diphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone,
4,4′-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-
Diaminotoluene, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, o-tolidine, 4,4 ″ -diaminoterphenyl, 1,5-diaminonaphthalene, 3,3′-dimethyl-4, 4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-
Aminophenoxy) phenyl] ether, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone and the like. When a fluorine-based material is used, a polyamic acid that can be converted into a film having good transparency in a short wavelength region can be obtained.
-Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like.

When siloxane diamine is used as a part of the diamine, the adhesion to the inorganic substrate can be improved. The siloxane diamine is usually used in an amount of 1 to 20 mol% of the total diamine. If the amount of siloxane diamine is too small, the effect of improving the adhesiveness will not be exhibited, and if it is too large, the heat resistance will decrease. Specific examples of the siloxane diamine include bis-3- (aminopropyl) tetramethylsiloxane. The present invention is not limited to this, and one or more diamines are used.

The synthesis of a polyamic acid is generally carried out by mixing and reacting a tetracarboxylic dianhydride and a diamine in a polar organic solvent. At this time, the degree of polymerization of the resulting polyamic acid can be adjusted by the mixing ratio of the diamine and the tetracarboxylic dianhydride.

In addition, there are various methods for obtaining a polyamic acid, for example, by reacting tetracarboxylic acid dichloride with a diamine in a polar organic solvent, and then removing hydrochloric acid and the solvent to obtain a polyamic acid.

On the other hand, as the three primary color layers, a layer in which a dye is dispersed in a resin can be used. Pigment 3
Any suitable combination can be used to represent the primary colors. Dyes that can be used include red, orange, yellow,
Examples include, but are not limited to, pigments and dyes such as green, blue, and purple. In addition, as the resin, a transparent resin such as an acrylic resin or an epoxy resin can be used.However, in view of the heat resistance, light resistance, and solvent resistance of the coating film, as the resin,
Preferably, a polyamic acid is used.

The transparent electrode is usually made of indium tin oxide (ITO). The transparent electrode is necessary to drive the liquid crystal.However, in the liquid crystal display device of the display method of the lateral electric field drive, the transparent electrode is not necessary on the color filter side, so the color filter without the transparent electrode is used. Is done.

The liquid crystal display of the present invention is characterized by using the color filter of the present invention. By using the color filter of the present invention, in the liquid crystal display device, it is possible to prevent the occurrence of display failure due to the unevenness of the color filter surface, and also to prevent the display failure due to the optical anisotropy of the overcoat. It is possible to do. Since the color filter of the present invention is used for a color liquid crystal display device, it is preferable to use a thin film transistor (TFT) for driving the liquid crystal display device of the present invention.

[0055]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 65.05 g of trimellitic acid was added to γ-butyrolactone.
After dissolving in 280 g, 74.95 g of γ-aminopropyltriethoxysilane was added and heated at 120 ° C. for 2 hours. To 20 g of the obtained solution, 7 g of bisphenoxyethanol full orange glycidyl ether and 15 g of diethylene glycol dimethyl ether were added,
The mixture was stirred at room temperature (about 23 ° C.) for 2 hours to obtain a thermosetting resin solution composition for a color filter (A1).

Comparative Example 1 In place of 7 g of bisphenoxyethanol full orange glycidyl ether, the epoxy equivalent was 180 to 190.
A thermosetting resin solution composition for a color filter (B1) was obtained in the same manner as in Example 1, except that 2.4 g of the bisphenol A type epoxy compound was used.

Example 2 A color filter was prepared by the following steps.

(Preparation of Resin Black Matrix Layer) A 20 L reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot / cooling water, and a stirring device was charged with γ-
Butyrolactone 16644.1 g, 4,4′-diaminodiphenyl ether 600.7 g, 3,3′-diaminodiphenyl sulfone 670.2 g, bis-3-
(Aminopropyl) tetramethylsiloxane 74.6
g and the kettle was heated to 30 ° C. 30 minutes later,
644.4 g of 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride 64
1.3 g and 294.2 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were added, and the kettle was heated to 58 ° C. Three hours later, 11.8 g of maleic anhydride was added, and the mixture was further heated at 58 ° C for 1 hour to obtain a polyamic acid NMP solution (A2).

Using a homogenizer together with 4.6 g of carbon black, 24.0 g of a polyamic acid solution (A2) and 61.4 g of N-methylpyrrolidone and 90 g of glass beads for 30 minutes at 7000 rpm,
The glass beads were removed by filtration to obtain a carbon black mill base.

Pigment Blue 15: 6 2.2
g, 24.0 g of polyamic acid solution (A2) and 63.8 g of N-methylpyrrolidone with 90 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration to obtain a blue pigment mill base. .

By mixing all of the obtained mill bases in total, a paste for a resin black matrix was obtained.

A paste for a resin black matrix was spin-coated on an alkali-free glass substrate (0.7 mm thick), and then dried at 50 ° C. for 10 minutes, at 90 ° C. for 10 minutes and at 110 ° C. for 20 minutes using an oven. And dried by heating to obtain a 1.3 μm-thick polyimide precursor colored film. A positive photoresist (OFPR-80 manufactured by Tokyo Ohka Co., Ltd.) is formed on this film.
0) and dried by heating at 80 ° C. for 20 minutes.
m was obtained. Ultraviolet light having an intensity of 50 mJ / cm ² at a wavelength of 365 nm was irradiated through a chrome photomask using an ultraviolet exposure apparatus PLA-501F manufactured by Canon Inc. After the exposure, the substrate was immersed in a developing solution consisting of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide to simultaneously develop the photoresist and the polyimide precursor colored film. After the etching, the unnecessary photoresist layer was stripped with methyl cellosolve acetate. Further, the polyimide precursor colored film thus obtained was heat-treated at 300 ° C. for 30 minutes in a nitrogen atmosphere to obtain a 1.0 μm-thick polyimide colored pattern film.

(Preparation of Colored Layer) Next, Pigment Red 177, Pigment Green 36, and Pigment Blue 15: 6 were prepared as red, green, and blue pigments, respectively.
It was mixed and dispersed with the polyamic acid solution (A2) to obtain three kinds of colored pastes of red, blue and green.

The obtained red paste was spin-coated on a resin black matrix substrate, and dried at 50 ° C. for 10 minutes.
The film was dried by heating in an air at 110 ° C. for 10 minutes and at 110 ° C. for 20 minutes to obtain a 1.2 μm-thick polyimide precursor colored film. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Co., Ltd.) is applied on this film,
After drying for 1 minute, a resist film having a thickness of 1.1 μm was obtained.
Using a UV exposure machine PLA-501F manufactured by Canon Inc., a wavelength of 365 nm through a chrome photomask.
UV light with an intensity of 50 mJ / cm ² was applied. After the exposure, the substrate was immersed in a developing solution consisting of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide to simultaneously develop the photoresist and the polyimide precursor colored film. After the etching, the unnecessary photoresist layer was stripped with methyl cellosolve acetate. Further, the thus obtained polyimide precursor colored film was heat-treated at 300 ° C. for 30 minutes in a nitrogen atmosphere to obtain a 1.0 μm-thick polyimide red pattern film.

Thereafter, similarly, a pattern of a green paste and a blue paste was formed to obtain a color filter having three primary colors of red, green and blue.

(Formation of Overcoat Layer) The thermosetting resin solution composition (A) for a color filter obtained in Example 1
1) was spin-coated on the color filter, and 100
By heating at 260C for 5 minutes and at 260C for 30 minutes, an overcoat having a thickness of 1.0 m was obtained.

As a result of observing the surface shape of the obtained color filter using Surfcom 1500A manufactured by Tokyo Seimitsu Co., Ltd., the surface was very flat and the largest step was 0.18 μm.

Further, the optical anisotropy of the overcoat film was measured using a polarization analyzer AEP-100 manufactured by Shimadzu Corporation for the portion of only the glass substrate of the color filter. Incident angle 4
0 °) was 0.2 nm, indicating that there was almost no optical anisotropy.

Further, in the obtained color filter, defects due to sublimates and evaporates were not observed.

(Preparation of Liquid Crystal Display) Further, after the obtained color filter was washed with a neutral detergent, an alignment film made of a polyimide resin was applied by a printing method, and heated at 250 ° C. for 10 minutes on a hot plate. Thickness is 0.07μ
m. Thereafter, the color filter substrate was subjected to a rubbing treatment, a sealant was applied by a dispense method, and heated on a hot plate at 90 ° C. for 10 minutes.

On the other hand, the substrate on which the TFT array is formed on the glass is similarly washed, and then an alignment film is applied and heated. Thereafter, a spherical spacer having a diameter of 5.5 μm is sprayed thereon, and the spacer is overlapped with the color filter substrate, and heated at 160 ° C. for 90 minutes while pressurizing in an oven to cure the sealant. The cell was heated at 120 ° C. and 13.3 Pa for 4 hours.
Subsequently, after allowing to stand for 0.5 hour in nitrogen, liquid crystal injection was performed again under vacuum. The liquid crystal injection was performed by placing the cell in a chamber, reducing the pressure to 13.3 Pa at room temperature, immersing the liquid crystal injection port in the liquid crystal, and returning the pressure to normal pressure using nitrogen. After the injection of the liquid crystal, the liquid crystal injection port was sealed with an ultraviolet curable resin. Next, a polarizing plate was attached to the outside of the two glass substrates of the cell to complete the cell. further,
The obtained cell was modularized to complete a liquid crystal display device driven by a lateral electric field. Observation of the obtained liquid crystal display device revealed no display failure.

Example 3 A transparent electrode was applied to the color filter obtained in Example 2 in the following steps.

(Formation of Transparent Electrode Layer) When an ITO film was formed on the overcoat by a sputtering method, the thickness was 1400 angstroms and the surface resistance was 15 Ω /
□ ITO was obtained.

As a result of observing the surface shape of the obtained color filter in the same manner as in Example 2, the surface was very flat, and the largest step was 0.18 μm.
Met.

Using the obtained color filter, a liquid crystal display device was prepared in the same procedure as in Example 2, but no display defect was found.

Comparative Example 2 A color filter was prepared in the same manner as in Example 2 except that the thermosetting resin solution composition for a color filter (B1) obtained in Comparative Example 1 was used as an overcoat.

As a result of observing the surface shape of the obtained color filter in the same manner as in Example 2, the surface was very flat, and the largest step was 0.19 μm.
Met.

However, when the optical anisotropy of the overcoat was measured in the same manner as in Example 2, it was found that the retardation was 1.5 nm and the optical anisotropy was large.

Further, in the obtained color filter, defects due to sublimates and evaporates were observed. The defect was void-shaped, and 20 or more defects were observed in the color filter surface.

Further, a liquid crystal display device was prepared in the same procedure as in Example 2 using the obtained color filter. However, display defects such as different colors between the left and right sides of the liquid crystal display device were observed.

Example 4 When preparing a color filter in the same manner as in Example 2, the thickness of each colored layer was set to 1.8 μm, and a spacer was formed on the resin black matrix simultaneously with the formation of each colored layer. Color filters were created. In addition,
The formed spacer has a form in which three primary colors are stacked.

As a result of observing the surface shape of the obtained color filter in the same manner as in Example 2, the surface was very flat and the largest step was 0.16 μm.
Met.

When the optical anisotropy of the overcoat was measured in the same manner as in Example 2, it was found that the retardation was 0.2 nm and there was almost no optical anisotropy.

Further, in the obtained color filter, no defects due to sublimates and evaporates were observed.

Further, a liquid crystal display device was prepared in the same procedure as in Example 2 except that the application of the spacers was stopped using the obtained color filter, but no display failure based on the color filter was observed. .

[0087]

Since the present invention is configured as described above, it is possible to provide an overcoat having no optical anisotropy for improving the flatness of the surface of the color filter without coating defects due to sublimation and evaporation of the constituent components. A thermosetting resin solution composition for a color filter can be provided.
Further, by using the color filter of the present invention, it is possible to prevent the occurrence of display failure based on the color filter in the liquid crystal display device.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H048 BA48 BB28 BB37 BB44 2H091 FA02Y FA08X FA08Z FA34Y FA35Y FB03 FB12 FC10 FC12 FC22 FC23 GA03 GA06 GA08 GA13 GA16 HA18 LA12

Claims (13)

[Claims] 1. A compound having at least one of alkoxysilane, silanol, and silanol condensate and a carboxylic acid in the same molecule, and a group having a planar structure having a molecular weight in the range of 70 to 1000 as a side chain. A thermosetting resin solution composition for a color filter, comprising: an epoxy compound having the same. 2. The compound having at least one of alkoxysilane, silanol and silanol condensate and a carboxylic acid in the same molecule has a molecular weight in the range of 200 to 1,000. Thermosetting resin solution composition for color filters. 3. The compound according to claim 1, wherein the compound having at least one of alkoxysilane, silanol, and silanol condensate and a carboxylic acid in the same molecule has a molecular weight in the range of 300 to 500. Thermosetting resin solution composition for color filters. 4. The compound having at least one of alkoxysilane, silanol, and silanol condensate and a carboxylic acid in the same molecule is a reaction product of an aminoalkoxysilane and an acid anhydride. Item 4. The thermosetting resin solution composition for a color filter according to any one of Items 1 to 3. 5. The thermosetting resin solution composition for a color filter according to claim 4, wherein the acid anhydride is trimellitic anhydride. 6. The thermosetting resin solution composition for a color filter according to claim 1, wherein the group having a planar structure is a fluorene group. 7. The thermosetting resin solution composition for a color filter according to claim 1, wherein the epoxy compound has a structure represented by the following general formula (1). Embedded image (Wherein, R _{is, -O -, - OCH 2 CH} 2 O- are shown,
R ′ represents hydrogen or an alkyl group having 4 or less carbon atoms. ) 8. A color filter comprising an overcoat formed from the thermosetting resin solution composition for a color filter according to claim 1. 9. The color according to claim 8, wherein a part of the colored layer composed of three primary colors or a plurality of dot-like spacers formed by laminating all of them is provided on a part of the black matrix. filter. 10. The color filter according to claim 8, wherein the transparent electrode layer is provided on the overcoat. 11. The black matrix wherein a light-shielding agent is dispersed in a resin.
The color filter according to any one of the above. 12. A liquid crystal display device using the color filter according to any one of claims 8 to 11. 13. The liquid crystal display device according to claim 12, wherein the liquid crystal is driven by a thin film transistor.