JP2000086906A - Thermosetting resin solution composition, color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin solution composition suitable for prevention of development of display failure and prevention of development of coating failure in liquid display devices, and color filters and liquid display devices each using the thermosetting resin solution composition. SOLUTION: This thermosetting resin solution composition is obtained by including a thermosetting resin component and solvents wherein the solvents consist of two or more kinds of solvent component, and solvent(s) with a boiling point of >=190 deg.C account(s) for 30-60 wt.% of all the solvents, and the solubility at 25 deg.C of the thermosetting resin component per 100 g of the solvents is >=35 g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermosetting resin solution composition for forming a buffer coat for semiconductors, an interlayer insulating film, a passivation film, etc., and a color filter.
Although it relates to a liquid crystal display device, particularly suitable for forming an overcoat such as a color filter in a liquid crystal display device, a thermosetting resin solution composition having high flattening characteristics, and the overcoat is provided. The present invention relates to a color filter 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 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.

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

[0004]

However, in a conventional thermosetting resin solution composition, when a thermosetting resin solution is applied to a substrate by using a spin coater, the thickness of the film depends on the distance from the center of rotation. Is non-uniform, and this non-uniformity causes non-uniformity of the cell gap, that is, a problem that causes display failure of the liquid crystal display device. Furthermore, when the thermosetting resin solution applied on the substrate is heated to form an overcoat, unreacted thermosetting resin components are precipitated to cause cissing, which may result in coating defects.

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

[0006]

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

[0007] A thermosetting resin solution composition of the present invention is a thermosetting resin solution composition containing a thermosetting resin component and a solvent, wherein the solvent comprises two or more solvent components, and The ratio of the solvent component having a boiling point of 190 ° C. or higher to the total solvent is 30 to 60% by weight, and the solubility of the thermosetting resin component in 100 g of the solvent at 25 ° C. is 35 g or higher. Is what you do.

The color filter of the present invention comprises a black matrix formed on a light-transmitting substrate, a coloring layer composed of three primary colors, and an overcoat. It is characterized by being formed from the thermosetting resin solution composition of the invention.

Further, a liquid crystal display device of the present invention is characterized by using the color filter of the present invention.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have found that the following measures are effective for the above-mentioned problems (non-uniformity of film thickness, cissing) concerning the overcoat.

That is, the authors of the present invention provide a thermosetting resin solution composition containing a thermosetting resin component and a solvent, wherein the solvent comprises two or more solvent components, and has a boiling point of 190 ° C. The ratio of the above solvent components to the total solvent is 30 to 60% by weight, and the solvent 10
The present inventors have found that a thermosetting resin solution composition characterized in that the solubility of the thermosetting resin component at 25 ° C. with respect to 0 g is 35 g or more can provide an excellent overcoat that realizes the above measures, and the present invention. Reached.

When a thermosetting resin solution is applied to a substrate by using a spin coater, the thermosetting resin solution dropped at the center of the substrate spreads radially across the entire substrate with rotation. It is applied all over. Since the speed of the substrate increases as the distance from the rotation center increases, the evaporation of the solvent increases at the end of the substrate, and the fluidity of the thermosetting resin solution decreases. Therefore, according to the distance from the center of rotation,
The overcoat film thickness becomes uneven.

In order to prevent the film thickness from becoming non-uniform, a solvent having a high boiling point may be used to suppress evaporation of the solvent during coating. However, simply using a solvent having a high boiling point results in insufficient drying of the thermosetting resin solution in a drying step after application, and defects such as repelling and inclusion of foreign matter are likely to occur.
Therefore, the solvent of the present invention is composed of two or more solvent components, of which the ratio of the solvent component having a boiling point of 190 ° C. or more to the total solvent is 30 to 60% by weight, more preferably 35 to 60% by weight. It is necessary to be. The solvent component having a boiling point of 190 ° C. or more may be used as a mixture of two or more kinds.

Further, if the solvent contains a solvent having a very low boiling point, coating defects such as unevenness are likely to occur due to evaporation of the low boiling point solvent during spin coating. Therefore, the solvent components contained in the solvent of the present invention all have a boiling point of 14%.
It is more preferable that the temperature is 0 ° C. or higher.

A specific example of such a solvent is 3-methoxy-3-methyl-1-butanol (bp 174).
° C), 1,3-butanediol (bp 203 ° C),
Methyl-1,3-butanediol (bp 203 ° C.), 2
-Methyl-1,3-propanediol (bp 213
° C), 2-heptanone (bp 150.2 ° C), 4-heptanone (bp 144.1 ° C), cyclohexanone (bp
155.7 ° C.), diisobutyl ketone (bp 168.1)
° C), ethylene glycol monobutyl ether (bp1
70.2 ° C.), ethylene glycol dibutyl ether (bp 203.3 ° C.), diethylene glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol monobutyl ether (bp 230.4 ° C.), diethylene glycol dimethyl ether (bp 159.8 ° C.),
Diethylene glycol diethyl ether (bp 188.
4 ° C), dipropylene glycol monomethyl ether (bp 190 ° C), dipropylene glycol monoethyl ether (bp 197.8 ° C), triethylene glycol monomethyl ether (bp 249 ° C), triethylene glycol dimethyl ether (bp 216 ° C), 3-methoxybutyl Acetate (bp 172.5 ° C), 3-methoxy-3-methylbutyl acetate (bp 188)
° C), ethylene glycol monomethyl ether acetate (bp 144.5 ° C), ethylene glycol monoethyl ether acetate (bp 156.3 ° C), ethylene glycol monobutyl ether acetate (bp 19
1.5 ° C.), diethylene glycol monoethyl ether acetate (bp 217.4 ° C.), propylene glycol monomethyl ether acetate (bp 146 ° C.), propylene glycol monoethyl ether acetate (b
p158 ° C), γ-butyrolactone (bp 204 ° C),
N, N-dimethylformamide (bp 153.0 ° C.)
N, N-dimethylacetamide (bp 166.1 ° C.)
2-pyrrolidone (bp 245 ° C), N-methylpyrrolidone (bp 202 ° C), 1,2,3-trichloropropane (bp 156.9 ° C), o-chlorotoluene (bp15
9.3 ° C.), p-chlorotoluene (bp 162.0
° C), o-xylene (bp 144.4 ° C), o-diethylbenzene (bp 183.4 ° C), m-diethylbenzene (bp 181.1 ° C), p-diethylbenzene (bp
183.8 ° C), o-dichlorobenzene (bp 180.
5 ° C.), m-dichlorobenzene (bp 173.0 ° C.),
n-butylbenzene (bp 183.3 ° C.), sec-butylbenzene (bp 178.3 ° C.), tert-butylbenzene (bp 169.1 ° C.) and the like.

If the solubility of the thermosetting resin component in the solvent is low, unreacted thermosetting resin component precipitates when the thermosetting resin solution is heated to form an overcoat, which causes cissing. Becomes Therefore, at 25 ° C., 100 g of the solvent contains 35 g or more of the thermosetting resin component,
It is necessary to dissolve preferably 50 g or more, more preferably 70 g or more. The solvent is appropriately selected from the above specific examples or other solvents according to the thermosetting resin component.

The solubility in the present invention means that a solute (a thermosetting resin component in the present invention) is a solvent (a solvent in the present invention).
Means the limit of dissolution in water and is represented by the amount (gram number) of solute per 100 g of solvent. The measurement of the solubility in the present invention is performed as follows. Solvent 10 in a thermostat at 25 ° C.
A thermosetting resin component is added to 0 g. When a certain amount or more is added, the thermosetting resin component remains in the solution without being completely dissolved. The thermosetting resin solution at this time is a saturated solution, and the solubility can be calculated from the concentration of the saturated solution. Since the solubility generally varies depending on the temperature, the measurement needs to be performed under a constant temperature condition using a thermostat or the like.

The solid content concentration of the thermosetting resin solution composition of the present invention is preferably from 10 to 60% by weight, more preferably from 1 to 60% by weight, from the viewpoint of applicability within a range not exceeding the above-mentioned solubility.
5 to 50% by weight. The solid content concentration in the present invention refers to the concentration of components remaining as a film when the thermosetting resin solution composition is heated to form an overcoat film, based on the entire thermosetting resin solution composition. .

The thermosetting resin component of the thermosetting resin solution composition of the present invention is not particularly limited, but a compound containing at least one of an acid anhydride and a carboxylic acid,
It is preferable to use an epoxy compound. In this case, since the curing proceeds due to the reaction between the acid anhydride and / or the carboxylic acid and the epoxy group, shrinkage during curing is small,
Excellent flattening characteristics.

Further, the compound containing at least one of an acid anhydride and a carboxylic acid is at least one of an alkoxysilane, a silanol and a silanol condensate, and at least one of an acid anhydride and a carboxylic acid. The compound containing the seed and the same molecule in the same molecule, from the viewpoint of the adhesion between the glass substrate and the overcoat,
More preferred.

Further, for a compound containing at least one of alkoxysilane, silanol and condensate of silanol and at least one of acid anhydride and carboxylic acid in the same molecule, the compound having too high a molecular weight may be used. When the molecular weight is too low, a coating defect is likely to occur due to sublimation and evaporation of the thermosetting resin component during heating if the molecular weight is too low. It is preferably from 1,000 to 1,000, and more preferably from 300 to 500. By using a compound having such a molecular weight range, it becomes possible to obtain a thermosetting resin solution composition having good flattening characteristics and hardly causing coating defects.

The method for obtaining a compound containing at least one of alkoxysilane, silanol and silanol condensate and at least one of acid anhydride and carboxylic acid in the same molecule is not particularly limited. , A compound having an alkoxysilane and a compound having an acid anhydride and / or a carboxylic acid can be obtained by reaction, polymerization, or the like.
Since it is easy to control the molecular weight, it is preferably obtained by reacting an aminoalkoxysilane with an acid anhydride. In particular, considering the versatility and molecular weight of the material, as aminoalkoxysilanes, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N
-Β (aminoethyl) γ-aminopropyltrimethoxysilane, 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 a compound having a carboxylic acid and an acid anhydride in the same molecule or a compound having at least two or more acid anhydrides in the same molecule. It is preferable to use trimellitic anhydride in view of easiness and cost.

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 of the present invention, the epoxy compound is not particularly limited, and bisphenol A type epoxy, bisphenol F type epoxy, phenol novolak epoxy, cresol novolak epoxy, alicyclic epoxy compound and the like are used. Although it is possible, it is particularly preferable to use 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. Since the compound has a group having a planar structure in a side chain, it is necessary to reduce display defects due to optical anisotropy of the overcoat film in order to suppress the orientation of the cured polymer in the film surface. Becomes possible. Here, as for the molecular weight of the group having the planar structure, when the molecular weight is smaller than 70, the effect of suppressing the orientation is reduced, and when the molecular weight is larger than 1,000, the reactivity with the curing agent is reduced. , 70-1
000 is preferred. The group having a planar structure is not particularly limited, and polycyclic aromatics and the like can be used.

However, from the viewpoint of availability, a group having a planar structure having a molecular weight in the range of 70 to 1,000 is preferably a fluorene group. Further, from the viewpoint of availability, an epoxy compound represented by the following general formula (1) is preferred. Preference is given to using compounds.

[0026]

Embedded image (However, R represents —O— or —OCH ₂ CH ₂ O—, and R ′ represents hydrogen or an alkyl group such as a methyl group or an ethyl group.) In an epoxy compound having a fluorene group, a fluorene group Has the effect of suppressing coating defects due to sublimation and evaporation during heating.

In the thermosetting resin solution composition of the present invention, the mixing ratio of the compound containing at least one of an acid anhydride and a carboxylic acid in the same molecule and the epoxy compound is such that the acid anhydride and the carboxylic acid are mixed. 5 to 300 parts by weight of the epoxy compound, preferably 10 to 250 parts by weight, more preferably 20 to 2 parts by weight, based on 100 parts by weight of a compound containing at least one of the acids in the same molecule.
00 parts by weight. If the amount of the epoxy compound is too large, the curing of the epoxy compound becomes insufficient, and if the amount is too small, the toughness of the coating film decreases, which is not preferable.

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

Further, a surfactant can be added to the thermosetting resin solution composition of the present invention for the purpose of improving coating properties and drying properties. The amount of the surfactant is usually 0.01 to 10 parts by weight based on 100 parts by weight of the resin.
Parts by weight, preferably 0.03 to 1 part by weight. If the addition amount is too small, there is no effect of improving coating properties and drying properties,
Conversely, if it is too large, poor coating properties and a decrease in toughness of the coating film are caused.

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, and epoxy-modified silicone oil. Phenol, carboxy, modified silicone oils such as 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.

The color filter of the present invention comprises a black matrix formed on a light-transmitting substrate, a colored layer composed of three primary colors, and an overcoat. It is characterized by being formed from a thermosetting resin solution composition.

By using the thermosetting resin solution composition of the present invention as an overcoat, it is possible to obtain a color filter having good flatness and an overcoat free from coating defects such as cissing.

Further, by providing a part of a colored layer composed of three primary colors or a plurality of dot-like spacers formed by laminating all of them on a part of a black matrix, a spacer in a liquid crystal display device manufacturing process can be provided. Spraying is not required, which greatly contributes to improvement of the yield, which is preferable.

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, and 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, the black matrix formed of a metal thin film has a high manufacturing cost and causes a rise 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 ratio of the light-shielding agent to be contained 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, from the viewpoint of 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 the polyamic acid, for example, aliphatic or alicyclic tetracarboxylic dianhydrides can be used. 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 a tetracarboxylic dichloride with a diamine in a polar organic solvent, and then removing the hydrochloric acid and the solvent to obtain a polyamic acid.

On the other hand, as the colored layers of the three primary colors, those 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 uses the color filter of the present invention. By using the color filter of the present invention, in a liquid crystal display device, it is possible to prevent the occurrence of display failure due to unevenness of the surface of the color filter and uneven thickness of the overcoat. Further, since the color filter of the present invention is used for a color liquid crystal display device,
For driving the liquid crystal display device of the present invention, a thin film transistor (TFT) is preferably used.

[0054]

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 (Preparation of thermosetting resin solution composition) 65.05 g of trimellitic anhydride was added to γ-butyrolactone (bp 204).
C.) after dissolving in 280 g, adding 74.95 g of γ-aminopropyltriethoxysilane,
Heated for hours. To 20 g of the obtained solution, 7 g of bisphenoxyethanol full orange glycidyl ether,
Diethylene glycol dimethyl ether (bp 159.
8 ° C.) 31.20 g, γ-butyrolactone 10.13
g was added and stirred at room temperature (about 23 ° C.) for 2 hours to obtain a thermosetting resin solution composition (A1).

In A1, 42.9% of the solvent having a boiling point of 190 ° C. or higher accounts for 25% of the thermosetting resin component based on the solvent.
The solubility at ° C. was 122 g.

Next, a color filter was prepared by the following steps.

(Preparation of Resin Black Matrix) A 20 L reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot water / 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).

4.6 g of carbon black, 24.0 g of a polyamic acid solution (A2) and 61.4 g of N-methylpyrrolidone were dispersed together with 90 g of glass beads at 7000 rpm for 30 minutes using a homogenizer.
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, a paste for a resin black matrix was obtained.

A resin black matrix paste is spin-coated on an alkali-free glass substrate (0.7 mm thick), and is heated in the air using an oven at 50 ° C. for 10 minutes, at 90 ° C. for 10 minutes, and at 110 ° C. for 20 minutes. By heating and drying, a 1.3 μm-thick polyimide precursor colored film was obtained. 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, and a color filter having three primary colors of red, green and blue was obtained.

(Formation of Overcoat Layer) The 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 obtain a thickness of 1.0 μm. Overcoat.

In the obtained color filter, no unevenness of the overcoat film thickness was observed, and the surface was very flat. Also, no coating defects such as repelling were 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 2 A liquid crystal display device was prepared in the same procedure as in Example 1 except that a transparent electrode was provided on the overcoat in the following steps, but there was no display defect.

(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.

COMPARATIVE EXAMPLE 1 65.05 g of trimellitic anhydride was treated with diethylene glycol dimethyl ether (bp 159.8 ° C.) 280
After dissolving in 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, 30.33 g of diethylene glycol dimethyl ether, and 11.00 g of γ-butyrolactone (bp 204 ° C.) were added.
The mixture was stirred at room temperature (about 23 ° C.) for 2 hours to obtain a thermosetting resin solution composition (B1).

In B1, 20.1% of a solvent having a boiling point of 190 ° C. or higher represents 25% of a thermosetting resin component based on the solvent.
The solubility at ° C. was 131 g.

A color filter was prepared in the same manner as in Example 1 except that the thermosetting resin solution composition (B1) obtained above was used as an overcoat. In the obtained color filter, nonuniformity was observed in the film thickness of the overcoat.

Further, a liquid crystal display device was prepared in the same procedure as in Example 1 using the obtained color filter. However, display defects due to non-uniformity of the overcoat film thickness were observed.

Comparative Example 2 After dissolving 65.05 g of trimellitic anhydride in 280 g of γ-butyrolactone (bp 204 ° C.), 74.95 g of γ-aminopropyltriethoxysilane was added and heated at 120 ° C. for 2 hours. 20 g of the resulting solution
7 g of bisphenoxyethanol full orange glycidyl ether and o-dichlorobenzene (bp 180.
5 ° C) 42.28 g, γ-butyrolactone 6.62
g was added and stirred at room temperature (about 23 ° C.) for 2 hours to obtain a thermosetting resin solution composition (B2).

In B2, the solvent having a boiling point of 190 ° C. or higher accounts for 32.1% of the solvent and 25% of the thermosetting resin component based on the solvent.
The solubility at ° C. was 28 g.

A color filter was prepared in the same manner as in Example 1, except that the thermosetting resin solution composition (B2) obtained above was used as an overcoat. Although the obtained color filter had a uniform overcoat film thickness, coating defects due to repelling of the overcoat were observed.

Further, a liquid crystal display device was prepared in the same procedure as in Example 1 using the obtained color filter. However, display defects due to coating defects of the overcoat were observed.

Comparative Example 3 After dissolving 65.05 g of trimellitic anhydride in 280 g of γ-butyrolactone (bp 204 ° C.), 74.95 g of γ-aminopropyltriethoxysilane was added and heated at 120 ° C. for 2 hours. 20 g of the resulting solution
7 g of bisphenoxyethanol full orange glycidyl ether and 41.33 g of γ-butyrolactone were added thereto, and the mixture was stirred at room temperature (about 23 ° C.) for 2 hours to obtain a thermosetting resin solution composition (B3).

In B3, 100% of the solvent having a boiling point of 190 ° C. or more is 25% of the thermosetting resin component based on the solvent.
Was 130 g.

A color filter was prepared in the same manner as in Example 1 except that the thermosetting resin solution composition (B3) obtained above was used as the overcoat. In the obtained color filter, coating defects due to repelling were recognized because the overcoat had insufficient drying properties.

Further, a liquid crystal display device was prepared in the same procedure as in Example 1 using the obtained color filter, but a display defect due to a coating defect of the overcoat was observed.

Example 3 The same procedure as in Example 1 was carried out except that when forming the color filter, the thickness of each colored layer was 1.8 μm, and a spacer was formed on the resin black matrix simultaneously with the formation of each colored layer. A color filter was prepared in the same manner. 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 1, the surface was very flat, and there were no coating defects such as non-uniform film thickness and cissing. .

Further, a liquid crystal display device was prepared in the same procedure as in Example 1 except that the application of the spacers was stopped using the obtained color filter, but no display failure was observed.

[0087]

According to the present invention, as described above, the film thickness is uniform,
A thermosetting resin solution composition capable of forming an overcoat having excellent flattening characteristics without coating defects can be provided. Further, by using the color filter of the present invention, it is possible to prevent the occurrence of display failure due to the defect of the color filter in the liquid crystal display device.

Claims (17)

[Claims] 1. A thermosetting resin solution composition containing a thermosetting resin component and a solvent, wherein the solvent is composed of two or more solvent components and has a boiling point of 190 ° C. or higher. 30-60% by weight of solvent
And a solubility of the thermosetting resin component in 100 g of the solvent at 25 ° C. of 35 g or more. 2. The thermosetting resin solution composition according to claim 1, wherein each solvent component constituting the solvent has a boiling point of 140 ° C. or higher. 3. The thermosetting resin according to claim 1, wherein the thermosetting resin component contains a compound containing at least one of an acid anhydride and a carboxylic acid, and an epoxy compound. Resin solution composition. 4. A compound containing at least one of an acid anhydride and a carboxylic acid, wherein the compound contains at least one of an alkoxysilane, a silanol and a silanol condensate, and at least one of an acid anhydride and a carboxylic acid. The thermosetting resin solution composition according to claim 3, which is a compound containing a seed and the same in the same molecule. 5. A compound containing at least one of alkoxysilane, silanol and silanol condensate and at least one of acid anhydride and carboxylic acid in the same molecule having a molecular weight of 200 to 1000. The thermosetting resin solution composition according to claim 4, which is within the range. 6. A compound containing at least one of alkoxysilane, silanol and silanol condensate and at least one of acid anhydride and carboxylic acid in the same molecule having a molecular weight of 300 to 500. The thermosetting resin solution composition according to claim 4, which is within the range. 7. A compound containing at least one of alkoxysilane, silanol and a condensate of silanol and at least one of acid anhydride and carboxylic acid in the same molecule, comprises aminoalkoxysilane and acid anhydride. The thermosetting resin solution composition according to any one of claims 4 to 6, which is a reaction product of a product. 8. The thermosetting resin solution composition according to claim 7, wherein the acid anhydride is trimellitic anhydride. 9. The epoxy compound having a molecular weight of 70 to 1
The thermosetting resin solution composition according to any one of claims 3 to 8, wherein a compound having a group having a planar structure in the range of 000 as a side chain is used. 10. The thermosetting resin solution composition according to claim 9, wherein the group having a planar structure is a fluorene group. 11. The thermosetting resin solution composition according to claim 9, wherein the epoxy compound has a structure represented by the following general formula (1). Embedded image (However, R represents —O— or —OCH ₂ CH ₂ O—, and R ′ represents hydrogen or an alkyl group such as a methyl group or an ethyl group.) 12. A black matrix formed on a light-transmitting substrate, a colored layer having three primary colors, and an overcoat, wherein the overcoat is any one of claims 1 to 11. 7. A color filter formed from the thermosetting resin solution composition described in 1. above. 13. A color filter according to claim 12, wherein a plurality of dot-shaped spacers formed by laminating a part of a colored layer composed of three primary colors or all layers are provided on a part of a black matrix. . 14. The color filter according to claim 12, wherein the transparent electrode layer is provided on the overcoat. 15. The black matrix according to claim 12, wherein a light-shielding agent is dispersed in a resin.
4. The color filter according to any one of 4. 16. A liquid crystal display device using the color filter according to claim 12. 17. The liquid crystal display device according to claim 16, wherein the liquid crystal is driven by a thin film transistor.