JP2003287617A - Thermosetting resin solution composition for color filter, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter being excellent in flattening characteristics and heat resistance and having an overcoat with little optical anisotropy. <P>SOLUTION: A thermosetting resin solution composition for the color filter contains a compound including at least a kind of substance out of alkoxysilane, silanol and a silanol condensate and an acid anhydride within the identical molecule and an epoxy compound including a group with molecular weight in 70-1,000 range and with a planar structure on a side chain. <P>COPYRIGHT: (C)2004,JPO

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 in particular, it forms an overcoat such as a color filter in the liquid crystal display device. Suitable for high flattening characteristics and high heat resistance,
The present invention relates to a thermosetting resin solution composition for a color filter that gives a coating film having no optical anisotropy, a color filter provided with the overcoat, and a liquid crystal display device using the color filter.

[0002]

2. Description of the Related Art In recent years, many color liquid crystal display elements have been proposed in which a color filter for color separation is combined with a liquid crystal element. Here, the color filter is composed of a large number of picture elements each having pixels of three primary colors of red, green, and blue formed on a light-transmissive substrate as one picture element. In order to increase the height, a light-shielding region (black matrix) having a constant width is provided, and there is also a device in which an overcoat or a transparent electrode is arranged as necessary. The overcoat has the ability to flatten the surface of the color filter (flattening characteristics), the adhesiveness with the light-transmissive substrate that constitutes the lower layer, pixels, and the black matrix, and the adhesion with the transparent electrode that constitutes the upper layer. Properties, adhesiveness with the encapsulant for forming liquid crystal cells, blocking properties of pixel impurity components, smoothness, light resistance, wet 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 are required in the substrate bonding process at that time.

In particular, when the liquid crystal display device is required to have high performance such as a wide viewing angle and a high speed response, the flatness of the color filter is important, so that the flattening property of the overcoat is improved. Is desired. In addition, in order to improve the display quality of the liquid crystal display device, the film forming temperature of the transparent electrode may be raised or the forming temperature of the alignment film may be raised. In such a case, the overcoat has high heat resistance. Required. Furthermore, in a liquid crystal display device, when a wide viewing angle is required, it is desired that the overcoat be optically anisotropic.

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, in the conventional thermosetting resin solution composition for color filter, the flattening property is insufficient, and in the liquid crystal display device, the display defect due to the surface unevenness of the color filter may occur. It could happen. Further, the overcoat obtained from the conventional thermosetting resin solution composition for a color filter may have low heat resistance, particularly a glass transition temperature,
When the alignment film was formed, a change in appearance was observed in the overcoat, which sometimes caused display defects. Furthermore, 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 the liquid crystal display device, the viewing angle dependence is different between the left and right display devices. There were cases where defects occurred.

For example, in Japanese Patent Laid-Open No. 2000-9914, at least one of alkoxysilane, silanol, and silanol condensate, and a compound containing carboxylic acid in the same molecule and a molecular weight of 70 to 1000 are described. An overcoat obtained from a thermosetting resin solution composition for a color filter, which comprises an epoxy compound having a group having a planar structure in the range in its side chain is described. The overcoat is characterized by high flattening ability and low optical anisotropy, but since the curing proceeds due to the reaction of the carboxylic acid and the epoxy group, the crosslink density is low and there is a problem in heat resistance. In a liquid crystal display device using the used color filter, a display defect may occur.

The present invention overcomes the drawbacks of the prior art,
It is intended to provide a thermosetting resin solution composition for a color filter, which is suitable for preventing display defects in a liquid crystal display device, and a color filter and a liquid crystal display device using the thermosetting resin solution composition for a color filter. With the goal.

[0008]

In order to achieve the above object, the present invention has the following configuration. (1) A compound containing at least one kind of alkoxysilane, silanol, and silanol condensate, and a compound containing an acid anhydride in the same molecule, and a group having a planar structure with a molecular weight in the range of 70 to 1000 as a side chain. A thermosetting resin solution composition for a color filter, comprising:

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have described the above-mentioned problems (planarization characteristics, heat resistance, optical anisotropy) regarding overcoats.
For each of the above, the following measures were found to be effective.

That is, in order to improve the flattening property of the overcoat, the molecular weight of the constituent components of the thermosetting resin solution composition for a color filter is reduced, and
It is effective to reduce the shrinkage of the coating film in the curing reaction, and in order to improve the heat resistance, it is effective to improve the degree of crosslinking of the coating film. It has been found that preventing the in-plane orientation of the coating film is effective in reducing the optical anisotropy.

The present inventors have used, as a curing agent, a compound containing at least one of alkoxysilane, silanol, and silanol condensate and an acid anhydride in the same molecule, and have a molecular weight of 70 to 1,000. It was found that a thermosetting resin solution composition system for a color filter, which cures an epoxy compound containing a group having a planar structure in the side chain in a range, provides an excellent overcoat that satisfies all the above problems, The present invention has been reached.

The thermosetting resin solution composition for a color filter of the present invention is cured by the reaction of the acid anhydride and the epoxy group, so that the shrinkage at the time of curing is small and the flattening property is excellent. Further, acid anhydrides are known to have higher reactivity with epoxy groups than carboxylic acids, and are preferable for improving the degree of crosslinking of the coating film. The thermosetting resin solution composition for a color filter of the present invention may have poor storage stability because of its high reactivity. In such a case, a compound containing at least one of alkoxysilane, silanol, and a silanol condensate and an acid anhydride in the same molecule, and a planar structure having a molecular weight in the range of 70 to 1000 The problem can be avoided by separately storing the epoxy compounds containing a group in the side chain and mixing the two before use.

For compounds containing at least one of alkoxysilane, silanol, and silanol condensate and an acid anhydride in the same molecule, if the molecular weight is too high, the flattening property becomes poor. In addition, when the molecular weight is too low, sublimation / evaporation during heating is likely to occur. Therefore, the molecular weight range is 200 to 10
00 is preferable, and 300 to 500 is more preferable. By using a compound having such a molecular weight range, it becomes possible to obtain a thermosetting resin solution composition for a color filter having good flattening characteristics.

The method for obtaining a compound containing at least one of alkoxysilane, silanol and a silanol condensate and an acid anhydride in the same molecule is not particularly limited, and a compound having an alkoxysilane and an acid can be used. Although it can be obtained by reaction of a compound having an anhydride, polymerization, etc., because of easy availability of the compound and easy control of the molecular weight, a reaction of a compound containing an aminoalkoxysilane and a plurality of acid anhydrides It is preferable to obtain. In particular, considering the versatility of the material and the molecular weight, as aminoalkoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane
Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N
It is possible to use -β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

As the compound having a plurality of acid anhydrides, aromatic, aliphatic and alicyclic acid dianhydrides can be used. As a specific example, as the aromatic acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, 3,4,9,10 -Perylene tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3', 4,4'-biphenyltetra Carboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ", 4,4" -paraterphenyltetracarboxylic dianhydride, 3,3 ", 4,4 "-Metaterphenyltetracarboxylic dianhydride and the like, and aliphatic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and alicyclic Examples of the acid dianhydride of the system include 1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,3,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-
Bicyclohexene tetracarboxylic dianhydride, 1,2,
4,5-cyclohexanetetracarboxylic dianhydride,
1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione and the like can be used. However, from the viewpoint of improving heat resistance, it is preferable to use an aromatic or alicyclic acid dianhydride, and from the viewpoint of reducing the optical anisotropy, an aliphatic or alicyclic acid dianhydride is preferable. It is more preferable to use an alicyclic acid dianhydride that can achieve the two properties at the same time, since it is preferable to use the acid dianhydride. Among the alicyclic dianhydrides, from the ease of availability,
1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexenetetracarboxylic dianhydride , 1,2,4,5-cyclohexanetetracarboxylic dianhydride is preferably used, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride having excellent symmetry is used. Is most preferable from the viewpoint of heat resistance.

The above aminoalkoxysilane is
It can be used in a state of being reacted with an acid anhydride, but it can also be used in a state of hydrolyzed silanol or a hydrolyzed and condensed silanol condensate. Hydrolysis is performed by adding water to a reaction product of an aminoalkoxysilane and an acid anhydride and reacting at low temperature, and hydrolysis and condensation is performed by adding water to a reaction product of an aminoalkoxysilane and an acid anhydride and heating. By removing water and alcohol. Here, an acid catalyst may be added to the hydrolysis and the hydrolysis 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 contains a group having a planar structure in the range of up to 1000, 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 protruding from the main chain direction generated by the reaction between the epoxy group and the acid anhydride. Here, the molecular weight is 70 to 10.
Regarding the molecular weight of the group having a planar structure in the range of 00, when it is less than 70, the effect of suppressing the orientation becomes small, and when it is more than 1000, the reactivity with the curing agent decreases. Therefore, it is preferably in the range of 70 to 1000. Further, the group having a planar structure is not particularly limited, and a benzene ring, a polycyclic aromatic group, or the like can be used.

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

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

[0020]

[Chemical 2]

(However, R is --O--, --OCH ₂ CH ₂
Represents O-, and R'represents hydrogen or an alkyl group having 4 or less carbon atoms. In addition, in the epoxy compound containing a fluorene group, the presence of the fluorene group has an effect of suppressing sublimation / evaporation during heating.

In the thermosetting resin solution composition for a color filter of the present invention, alkoxysilane, silanol,
A compound containing at least one silanol condensate and an acid anhydride in the same molecule, and a molecular weight of 70 to 100
The mixing ratio of the epoxy compound containing a group having a planar structure in the range of 0 is 100 weight% of a compound containing at least one kind of alkoxysilane, silanol, and silanol condensate and an acid anhydride in the same molecule. 5 to 300 parts by weight of the epoxy compound, preferably 10 to 10 parts by weight.
250 parts by weight, more preferably 20 to 200 parts by weight. If the compound containing at least one of alkoxysilane, silanol, and silanol condensate and the acid anhydride in the same molecule is too small, the curing of the epoxy compound will be insufficient, and if too large, the coating film Is not preferable because the toughness of is decreased.

A curing catalyst may be added to the thermosetting resin solution composition for color filters of the present invention. As the curing catalyst, amines, imidazoles, metal chelates and the like can be used, but are not limited thereto.

As the solvent used in the thermosetting resin solution composition for a color filter of the present invention, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, Ethers such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl 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 Glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, esters such as γ- butyrolactone, N, N-
Examples thereof include amides such as 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 coating properties, solubility of constituent components, and the like, and they can be used alone or in combination of two or more. Further, the solid content concentration of the thermosetting resin composition of the present invention is from 5 to 70%, preferably from 8 to 60%, more preferably from 10 to 50% from the viewpoint of coating method and solubility. .

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

Specific examples of the surfactant include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, alkyl, fluorine-modified silicone oil, polyether, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil. , Phenol, carboxy, modified silicone oils such as mercapto modified silicone oil, anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, cationic surfactants such as lauryl trimethyl ammonium chloride, lauryl dimethyl Ampholytic 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 surfactants described above are not limited to these, and one kind or a combination of two or more kinds can be used.

The method for applying the thermosetting resin solution composition for a color filter of the present invention onto a substrate is 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 the substrate in the solution, and a method of spraying the solution on the 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 is composed of a black matrix formed on a light transmissive substrate, a colored layer consisting of three primary colors, and an overcoat, or is formed on a light transmissive substrate. A black matrix, a colored layer composed of three primary colors, a part of the colored layer composed of three primary colors on a part of the black matrix, or a plurality of dot-shaped spacers formed by stacking all of them, and an overcoat By using the thermosetting resin solution composition for a color filter of the present invention as an overcoat, an overcoat having good flatness and no optical anisotropy can be obtained by sublimation / evaporation. It can be obtained without any coating defects due to objects.

Here, the dot-shaped spacers do not require spacer dispersion in the liquid crystal display device manufacturing process and greatly contribute to the improvement of the yield. Further, the color filter of the present invention may be provided with a transparent electrode on the overcoat.

The components of the color filter of the present invention will be described. First, the light transmissive substrate is not particularly limited, and may be quartz glass, borosilicate glass, aluminosilicate glass, inorganic glass such as soda lime glass whose surface is silica-coated, or an organic plastic film or sheet. It is preferably used.

The black matrix is a light-shielding area between pixels and plays a role of improving the contrast of the liquid crystal display device, but is often formed of a metal thin film having a fine pattern. The metals include Cr, Ni,
Al or the like is used. As a method of forming a metal thin film,
The sputtering method, the vacuum deposition method, etc. are widely used. The fine pattern can be obtained by forming a photoresist pattern on the metal thin film by photolithography and then etching the metal thin film using the resist pattern as an etching mask.

However, the black matrix formed of the metal thin film has a high manufacturing cost, which causes a rise in the price of the color filter itself. Further, Cr, which is generally used as a metal thin film for a black matrix, has a high reflectance, so that there is a problem that the display quality is significantly deteriorated by the reflected light of Cr in a place where the external light is strong. Further, a method of providing a layer of chromium oxide between Cr and the light transmissive substrate in order to reduce the reflectance of the black matrix has been proposed, but it is not preferable from the viewpoint of manufacturing cost.

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

Examples of the light-shielding agent used in the resin black matrix include 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. The pigment mixture and the like can be used. Among these, carbon black is particularly preferable because it has excellent light-shielding properties.

When carbon black is used as the light-shielding agent, it is preferable to mix a pigment having a complementary color of carbon black in order to make the color tone achromatic. As the complementary color pigment, a blue pigment and a purple pigment may be used alone or in combination of both.
When carbon black and a pigment having a complementary color to carbon black are used as the light-shielding agent, in order to obtain high light-shielding property, the ratio of carbon black contained in the light-shielding agent is
It is preferably 50% by weight or more, more preferably 6
It is 0% by weight or more, 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 and 15:
1, 15: 2, 15: 3, 15: 4, 15: 6, 16,
21, 22, 60, 64 and the like are mentioned, but Pigment Blue 15, 15: 1, 15: 2 and 15: 6 are particularly preferable. Examples of purple pigments include pigment violet 19, 23, 29, 31, 32, 33, 36, 3
7, 39, 43, 50 and the like can be mentioned, but pigment violet 23, 31, 33, 43, 50 is particularly preferable.

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

The resin used for the resin black matrix may be a transparent resin such as an acrylic resin or an epoxy resin, but in view of the heat resistance, light resistance and solvent resistance of the coating film, the resin is: Preference is given to using polyimide.

The resin black matrix containing polyimide as a resin can be obtained by applying a resin black matrix paste containing polyamic acid to a light transmissive substrate and patterning.

The polyamic acid can be obtained by reacting an acid dianhydride with a diamine. As the dianhydride, for example, an aliphatic or alicyclic dianhydride 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, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-
3-furanyl) -naphtho [1,2-C] furan-1,3
-Zeon and the like. Further, when an aromatic type is used, a polyamic acid which can be converted into a film having good heat resistance can be obtained, and specific examples thereof include 3,3 ′,
4,4'-benzophenone tetracarboxylic dianhydride,
Pyromellitic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'-
Oxydiphthalic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ", 4,4"
-Paraterphenyl tetracarboxylic dianhydride, 3,
3 ″, 4,4 ″ -metaterphenyl tetracarboxylic acid dianhydride may be mentioned. Further, by using a fluorine-based one, it is possible to obtain a polyamic acid that can be converted into a film having good transparency in a short wavelength region, and as a specific example thereof,
4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride and the like can be mentioned. The present invention is not limited to these, and one or two or more acid dianhydrides are used.

As the diamine, for example, an aliphatic or alicyclic diamine can be used, and specific examples thereof include 1,3-diaminocyclohexane, 1,
4-diaminocyclohexane, 4,4'-diamino-
3,3'-Dimethyldicyclohexylmethane, 4,4 '
-Diamino-3,3'-dimethyldicyclohexyl and the like can be mentioned. When an aromatic type is used, a polyamic acid that can be converted into a film having good heat resistance can be obtained, and 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 can be mentioned. Further, when a fluorine-based one is used, a polyamic acid that can be converted into a film having excellent transparency in the short wavelength region can be obtained, and specific examples thereof include 2,2
-Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like.

When siloxane diamine is used as a part of the diamine, the adhesiveness with the inorganic substrate can be improved. The siloxane diamine is usually used in an amount of 1 to 20 mol% based on all diamines. 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 may be used.

The polyamic acid is generally synthesized by mixing an acid dianhydride and a diamine in a polar organic solvent and reacting them. At this time, the degree of polymerization of the obtained polyamic acid can be adjusted by the mixing ratio of the diamine and the acid dianhydride.

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

On the other hand, for the colored layers of the three primary colors, it is possible to use those in which a dye is dispersed in a resin. 3 pigments
Any suitable combination can be used to represent the primary colors. The pigments that can be used are red, orange, yellow,
Examples include, but are not limited to, pigments and dyes such as green, blue, and purple. Further, as the resin, it is possible to use a transparent resin such as an acrylic resin or an epoxy resin, but in view of the heat resistance, light resistance and solvent resistance of the coating film, the resin is:
Preference is given to using polyimide.

Indium tin oxide (ITO) is usually used for the transparent electrode. The transparent electrode is necessary to drive the liquid crystal, but in the liquid crystal display device of the horizontal electric field driving display type, the transparent electrode is not required on the color filter side, so a color filter without the transparent electrode is used. To be done.

The liquid crystal display device 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 defects due to the unevenness of the color filter surface, and to prevent the occurrence of display defects due to the optical anisotropy of the overcoat. It becomes possible to do. Further, since the color filter of the present invention is used in 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.

[0049]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. (Thermosetting resin solution composition for color filters (A1)
Preparation of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride 85.53 g of N-methylpyrrolidone
After dispersing in a mixed solvent of 170 g and 170 g of diethylene glycol methyl ethyl ether, 84.47 g of γ-aminopropyltriethoxysilane was added and heated at 60 ° C. for 2 hours. 20 g of the obtained solution was added with 15 bisphenoxyethanol full orange glycidyl ether.
g and N-methylpyrrolidone (12 g) were added, and 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). (Thermosetting resin solution composition for color filters (B1)
Preparation of bisphenoxyethanol full orange glycidyl ether Instead of 7 g, the epoxy equivalent is 180
-190 bisphenol A type epoxy compound 2.4
A thermosetting resin solution composition for a color filter (B1) was obtained in the same manner as in Example 1 except that g was used. (Thermosetting resin solution composition for color filters (B2)
Adjustment) After dissolving 65.05 g of trimellitic acid in 280 g of γ-butyrolactone, 74.95 g of γ-aminopropyltriethoxysilane was added, and 120 ° C
Heated for 2 hours. 20 g of the obtained solution was added with bisphenoxyethanol full orange glycidyl ether 7
g and 15 g of diethylene glycol dimethyl ether were added, and the mixture was stirred at room temperature (about 23 ° C.) for 2 hours to obtain a thermosetting resin solution composition (B2) for a color filter.

Example 1 A color filter was prepared by the following steps. (Creation of resin black matrix layer) Thermometer, dry nitrogen inlet, heating / cooling device with hot / cooling water, and
In a 20 L reaction kettle equipped with a stirrer, γ-butyrolactone 16644.1 g, 4,4′-diaminodiphenyl ether 600.7 g, 3,3′-diaminodiphenyl sulfone 670.2 g, bis-3- (aminopropyl) tetra 74.6 g of methyl siloxane was added and the kettle was heated to 30 ° C. After 30 minutes, 3,3 ', 4,4'-
Benzophenone tetracarboxylic dianhydride 644.4
g, pyromellitic dianhydride 641.3 g, 3,
294.2 g of 3 ', 4,4'-biphenyltetracarboxylic dianhydride was added and the kettle was heated to 58 ° C. After 3 hours, 11.8 g of maleic anhydride was added, and the mixture was heated at 58 ° C. for another hour to give N of polyamic acid.
An MP solution (A2) was obtained.

Carbon black (4.6 g), polyamic acid solution (A2) (24.0 g) and N-methylpyrrolidone (61.4 g) were dispersed together with glass beads (90 g) using a homogenizer at 7,000 rpm for 30 minutes.
The glass beads were removed by filtration to obtain a carbon black mill base.

Pigment Blue 15: 6 2.2
g, polyamic acid solution (A2) 24.0 g, N-methylpyrrolidone 63.8 g together with glass beads 90 g using a homogenizer, after the dispersion treatment at 7,000 rpm for 30 minutes, the glass beads were removed by filtration to obtain a blue pigment mill base. .

By mixing all the obtained mill bases, a paste for resin black matrix was obtained. The resin black matrix paste is spin-coated on a non-alkali glass substrate (thickness 0.7 mm), and the temperature is 1 at 50 ° C.
The polyimide precursor colored film having a thickness of 1.3 μm was obtained by heating and drying in air using an oven for 0 minutes, 90 ° C. for 10 minutes, and 110 ° C. for 20 minutes. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Co., Ltd.) is applied onto this film,
It was heated and dried at 80 ° C. for 20 minutes to obtain a resist film having a film thickness of 1 μm. Canon Inc. UV exposure machine PLA-501
Using F, through a chrome photomask, a wavelength of 36
It was irradiated with ultraviolet light having an intensity at 5 nm of 50 mJ / cm ² . After the exposure, the photoresist and the colored film of the polyimide precursor were developed at the same time by immersing in a developing solution composed of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. After etching, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate. Further, the polyimide precursor colored film thus obtained is heat-treated at 300 ° C. for 30 minutes in a nitrogen atmosphere,
A polyimide colored pattern film having a film thickness of 1.0 μm was obtained. (Creation of colored layer) Next, as red, green and blue pigments, Pigment Red 177 and Pigment Green 3 respectively.
6 and Pigment Blue 15: 6 were prepared and 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 the mixture was heated at 50 ° C. for 10 minutes for 90 minutes.
The polyimide precursor colored film having a thickness of 1.2 μm was obtained by heating and drying in air using an oven at 10 ° C. for 10 minutes and 110 ° C. for 20 minutes. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied onto this film, and the photoresist is applied at 80 ° C.
The resist film having a film thickness of 1.1 μm was obtained by heating and drying for 1 minute.
Using a UV exposure machine PLA-501F manufactured by Canon Inc., a wavelength of 365 nm through a photomask made of chromium.
UV light having an intensity of 50 mJ / cm ² was irradiated. After the exposure, the photoresist and the colored film of the polyimide precursor were developed at the same time by immersing in a developing solution composed of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. After etching, the unnecessary photoresist layer was peeled off 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 polyimide red pattern film having a film thickness of 1.0 μm.

Thereafter, in the same manner, a pattern of green paste and blue paste was formed to obtain a color filter having three primary colors of red, green and blue. (Preparation of overcoat layer) The color filter thermosetting resin solution composition (A1) was spin-coated on the color filter and heated at 100 ° C. for 5 minutes and at 260 ° C. for 30 minutes to give a thickness of 1.0 μm. It was an overcoat of.

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. In addition, using the powder obtained by scraping the obtained overcoat from the substrate as a sample, TA
The glass transition temperature was measured by a differential scanning calorimetry method (heating temperature: 0 to 280 ° C., temperature rising rate: 5 ° C./min) using DSC2920 manufactured by INSTRUMENTS.
No glass transition temperature was observed, indicating that the overcoat film had high heat resistance.

Further, the METRI was applied to the overcoat coating film only on the glass substrate of the color filter.
When the optical anisotropy was measured using a prism coupler MODEL 2010 manufactured by CON, it was found that the retardation (incident angle 40 °) was 0.1 nm, and there was almost no optical anisotropy.

No defects due to sublimates or evaporants were observed in the obtained color filter.

The obtained overcoat was scraped off and subjected to IR measurement by the potassium bromide tablet method using a Fourier transform infrared spectrophotometer manufactured by Horiba, Ltd., and it was found that absorption based on ether derived from fluorene, siloxane, and epoxy. I could observe. (Preparation of transparent electrode layer) An ITO film was formed on the overcoat by a sputtering method. The film forming temperature was 230 ° C. As a result, the film thickness is 1400 angstroms,
ITO having a surface resistance of 15Ω / □ was obtained. (Preparation of liquid crystal display device) Further, after the obtained color filter is washed with a neutral detergent, an alignment film made of a polyimide resin is applied by a printing method, and a hot plate is used to form 250
Heated at 10 ° C for 10 minutes. The film thickness was 0.07 μm.
After that, the color filter substrate is rubbed, a sealant is applied by a dispensing method, and a hot plate is used to
Heated at 0 ° C. for 10 minutes.

On the other hand, after similarly cleaning the substrate on which the TFT array is formed on the glass, an alignment film is applied and heated. After that, spherical spacers having a diameter of 5.5 μm are scattered, overlapped with the color filter substrate, and heated at 160 ° C. for 90 minutes while applying pressure in an oven to cure the sealant. This cell was heated at 120 ° C. and 13.3 Pa for 4 hours,
Then, after leaving in nitrogen for 0.5 hour, liquid crystal was injected again under vacuum. The liquid crystal was injected 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 to normal pressure with nitrogen. After the liquid crystal was injected, 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. As a result of observing the obtained liquid crystal display device, it was found that there was no display defect.

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

The surface shape of the obtained color filter was observed in the same manner as in Example 1. As a result, the surface was very flat, and the largest step was 0.20 μm.
Met. Further, the glass transition temperature measured in the same manner as in Example 1 was 265 ° C., and it was found that the glass transition temperature was relatively high.

However, when the optical anisotropy of the overcoat was measured in the same manner as in Example 1, it was found that the retardation was 1.5 nm and the optical anisotropy was large. Also, the obtained color filter,
Defects due to sublimates and evaporates were observed. The defects were voids, and 20 or more defects were observed on the surface of the color filter.

Further, using the obtained color filter, a liquid crystal display device was produced by the same procedure as in Example 1. However, display defects such as different colors on the left and right sides of the liquid crystal display device were observed.

Comparative Example 2 A color filter was prepared in the same manner as in Example 1 except that the thermosetting resin solution composition for a color filter (B2) obtained in Comparative Example 2 was used as the overcoat. The surface shape of the obtained color filter was observed in the same manner as in Example 1. As a result, the surface was very flat, and the largest step was 0.19 μm. Further, when the optical anisotropy of the overcoat was measured in the same manner as in Example 1, the retardation was 0.
It was 2 nm, and it was found that the optical anisotropy was relatively small.

However, the glass transition temperature measured in the same manner as in Example 1 was 195 ° C., which was inferior in heat resistance. In addition, the obtained color filter has ITO
Wrinkle-like defects occurred on the surface of the color filter during film formation. Further, using the obtained color filter, a liquid crystal display device was produced by the same procedure as in Example 2, but a display defect due to wrinkles of the color filter was observed.

Example 2 When a color filter was prepared in the same manner as in Example 1, the color layers were all made to have a thickness of 1.8 μm, and a spacer was formed on the resin black matrix simultaneously with the formation of each color layer. I made a color filter. In addition,
The formed spacer has a form in which the three primary colors are laminated.

The surface shape of the obtained color filter was observed in the same manner as in Example 1. As a result, the surface was very flat, and the largest step was 0.16 μm.
Met. Further, when the optical anisotropy of the overcoat was measured in the same manner as in Example 2, it was found that the retardation was 0.1 nm and there was almost no optical anisotropy. In addition, no defects due to sublimated substances or evaporated substances were observed in the obtained color filter.

Further, a liquid crystal display device was produced by using the obtained color filter in the same procedure as in Example 1 except that the spraying of the spacer was stopped, but no display defect due to the color filter was observed. .

[0070]

EFFECTS OF THE INVENTION Since the present invention is constructed as described above, it is possible to improve the flatness of the surface of the color filter, and to provide an overcoat having excellent heat resistance and no optical anisotropy. A curable resin solution composition can be provided. Further, by using the color filter of the present invention, it becomes possible to prevent the occurrence of display defects due to the color filter in the liquid crystal display device.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 183/08 C09D 183/08 G02F 1/1335 505 G02F 1/1335 505 F term (reference) 2H048 BA02 BA45 BB28 BB42 2H091 FA02Y FB01 FB03 FB07 FC02 FC13 FC22 FC23 FC26 FC29 GA01 GA02 GA03 GA08 GA09 GA13 KA02 LA17 LA19 LA30 4J036 AD11 DB17 DC06 DD08 JA15 4J038 DB021 DL031 DL081 GA06 JA42 KA03

Claims (9)

[Claims] 1. A compound containing at least one of an alkoxysilane, a silanol, and a silanol condensate and an acid anhydride in the same molecule, and a group having a planar structure having a molecular weight in the range of 70 to 1,000. A thermosetting resin solution composition for a color filter, which comprises an epoxy compound having a chain. 2. The compound containing at least one of alkoxysilane, silanol, and silanol condensate and an acid anhydride in the same molecule has a molecular weight in the range of 200 to 1,000. The thermosetting resin solution composition for a color filter according to 1. 3. A compound containing at least one of an alkoxysilane, silanol and a silanol condensate and an acid anhydride in the same molecule is a reaction product of an aminoalkoxysilane and a compound having a plurality of acid anhydrides. The thermosetting resin solution composition for a color filter according to claim 1 or 2, wherein 4. The thermosetting resin solution composition for a color filter according to claim 3, wherein the compound having a plurality of acid anhydrides is an alicyclic acid dianhydride. 5. The alicyclic acid dianhydride is 1,2,4,5-
The thermosetting resin solution composition for a color filter according to claim 4, which is cyclohexanetetracarboxylic dianhydride. 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). [Chemical 1] (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 having an overcoat formed from the thermosetting resin solution composition for a color filter according to claim 1. 9. A liquid crystal display device using the color filter according to claim 8.