JPH09325208A - Thermosetting resin composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin composition usable even in a continu ous ink jet method by which the pattern of a protective film is easily formed by composing the composition of a solvent component and a resin component, incorporating a specified ammonium compd. and controlling the resistance value below a specified value. SOLUTION: This thermosetting resin composition consists of a solvent component and a resin component, contains an ammonium compd. shown by R*4 N<+> X<-> and has <=1×10<5> Ω.cm resistance value. In the formula, N is nitrogen atom, R<+> is org. groups or hydrogen atom, X<-> is anions, and X<-> should be hydroxyl ion and R<+> methyl or ethyl. The resistance value is preferably controlled to <=5×10<4> Ω.cm and more preferably to <=1×10<4> Ω.cm. Further, the resin component preferably contains a compd. obtained by the reaction of an alkoxysilane having an amine group with a polycarboxylic anhydride.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting resin composition and a color filter, and more specifically, it is preferably used for producing a protective film, a flattening film, etc. of a color filter, and particularly an inkjet method. The present invention relates to a thermosetting resin composition and a color filter capable of forming a pattern by the method.

[0002]

2. Description of the Related Art In recent years, a color liquid crystal display device which can be applied to a personal computer, a word processor, a measuring instrument, a color television, etc. has been receiving attention. The structure of a liquid crystal cell of a conventional color liquid crystal display device, particularly a thin film transistor (TFT) type color liquid crystal display device is basically composed of a substrate having a color filter and a counter substrate having electrodes formed on a transparent substrate. Is. Here, as a usual manufacturing method of a color filter, first, a black matrix is formed on a transparent substrate, and then pixels of red (R), green (G), and blue (B) are formed by a photolithography method, and then, if necessary, this is formed. The top coat agent is applied by spin coating and heat-cured to form a protective film. This protective film functions to flatten the steps of pixels and smooth the surface, and to lower the resistance of the transparent conductive film on the protective film,
It improves the pixel contrast ratio, prevents scratches in the manufacturing process of liquid crystal display devices after forming a protective film as a protective film for pixels and a black matrix, and prevents impurity diffusion from the pixel to the liquid crystal after the liquid crystal is injected into the cell. Is effective for. However, since the formation of the protective film covers the entire surface of the color filter, liquid crystal display such as poor adhesion to the glass part, poor adhesion to the cell liquid crystal sealant, and poor adhesion to the cell external electrode. It also has a problem that becomes a factor of lowering device reliability. Therefore, in the TFT type color liquid crystal display device having a relatively large cell gap, it is often the case that the formation of the protective film is omitted, but the cell gap is shortened due to the high-speed response, and further, the transparent substrate is not used. In a color liquid crystal display device driven by an electric field in a parallel direction (horizontal electric field), formation of a protective film as a flattening film is expected, and it is expected that the protective film also has a function as an alignment film. Has been done. As a means for avoiding the problems in forming the protective film as described above, patterning of the protective film is considered, and it is desired to form the protective film that covers only the pixel portion of the color filter, but it is appropriate from the viewpoint of protective film characteristics and cost. The current situation is that no coating method has been found. Furthermore, in the manufacture of liquid crystal cells of liquid crystal display devices, a transparent conductive film is formed on a protective film and then an alignment film is applied. The alignment film has been applied by a conventional flexographic printing method. However, there is a problem that fine foreign matter contamination is likely to occur due to direct application by contact and repeated use of the application solution, or the application property is not sufficient, and an alignment film application method that can replace this flexographic printing method is expected. .

[0003]

The present invention was devised in view of the above-mentioned drawbacks of the prior art. An object of the present invention is to provide an ink jet method capable of easily forming a pattern of a protective film. The object of the present invention is also to provide a thermosetting resin composition for forming a transparent protective film that can be used even in the nuis method.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
A thermosetting resin composition comprising a solvent component and a resin component, containing an ammonium compound represented by the formula (1),
A thermosetting resin composition for a transparent protective film, which has a resistance value of less than 1 × 10 ⁵ Ω · cm.

[0005] _{^{R * 4 N + X - (}} 1) (N is a nitrogen atom, R ^* is an organic group or a hydrogen atom, X ^- represents an anion.)

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The thermosetting resin composition in the present invention does not contain a pigment component or a dye component added for the purpose of coloring.

The term "transparent" of the transparent protective film in the present invention does not mean that it is completely uncolored, but also includes the case where it is colored to some extent under the influence of a resin component, a solvent component and the like.

The resistance value of the thermosetting resin composition in the present invention is preferably smaller than 1 × 10 ⁵ Ω · cm, more preferably smaller than 5 × 10 ⁴ Ω · cm, and further preferably 1 It is less than × 10 ⁴ Ω · cm.

As the solvent component in the present invention, ethanol, methanol, isopropanol, butanol, 3
-Methoxy 3-methylbutanol, butyl cellosolve,
Examples thereof include alcohols such as methyl cellosolve and ethyl cellosolve, aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, and mixtures thereof, but are not limited thereto.

The ammonium compound in the present invention is represented by the following formula (1).

R ^* ₄ N ⁺ X ⁻ (1) In this formula, N is a nitrogen atom, R ^* is an organic group or a hydrogen atom, and X ⁻ is an anion.

The organic group in the present invention is not particularly limited, but preferred examples are an alkyl group, an allyl group,
An aryl group, an alkenyl group, an alkynyl group, a fluoroalkyl group, a benzyl group and the like can be mentioned, and an alkyl group, a benzyl group and a phenyl group are more preferable.
Preferred specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples thereof include isobutyl group, t-butyl group, and n-pentyl group, and more preferable examples include methyl group and ethyl group.

The anion in the present invention includes all anions and is not particularly limited. Specific examples of the anion include hydroxide ion, chloride ion, fluoride ion, bromide ion, iodide ion, nitrate ion, sulfate ion, oxalate ion, cyanide ion, and the like, and preferably hydroxylation. It is a product ion.

Specific examples of the ammonium compound in the present invention include tetramethylammonium hydroxide, tetraethylammonium hydroxide, dimethylethylbenzylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, methyltriethylammonium hydroxide and the like. Examples thereof include tetramethylammonium hydroxide and tetraethylammonium hydroxide. These ammonium compounds may be added as they are or in the form of a solution of water or a solvent. The content of the ammonium compound based on the total weight of the thermosetting resin composition is not particularly limited.

Examples of the alkoxysilane having an amino group in the present invention include an alkoxysilane having an amino group represented by the general formula Rn Si (OR ') 4-n.

In the formula, R and R'represent hydrogen or an organic group. Examples of the organic group include an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, and a fluoroalkyl group. More specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, neohexyl group, vinyl group, allyl group, isopropenyl group , Ethynyl group, 2-propynyl group, 3,3,3-trifluoropropyl group, γ-glycidoxypropyl group, methacryl group,
Examples thereof include γ-methacryloxypropyl group, phenyl group and tolyl group.

However, at least one of R is a group containing a primary amino group and / or a secondary amino group. The group containing a primary amino group, a γ-aminopropyl group,
Examples thereof include aminoethyl group, p-aminophenyl group, m-aminophenyl group and o-aminophenyl group. Examples of the group containing a secondary amino group include N-phenyl-γ-aminopropyl group, N-methyl-γ-aminopropyl group, N
-Ethyl-γ-aminopropyl group and the like. Among these groups containing a primary amino group and / or a secondary amino group, preferred are γ-aminopropyl group and p-aminopropyl group.
An aminophenyl group and the like.

R and R'may be the same or different. n is a number from 1 to 3.

Such a general formula Rn Si (OR ') 4-n
Specific examples of the alkoxysilane having an amino group represented by: γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-
Aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldiethylethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-
Aminopropylethyldimethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropylethylmethoxyethoxysilane, γ-aminopropylethylmethylethoxysilane, γ-aminopropylethylmethylmethoxysilane, N-β (aminoethyl) γ- Aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N
-Β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenylγ-amino Propyltrimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-
Aminophenylmethyldiethoxysilane, p-aminophenylethyldimethoxysilane, p-aminophenylethyldiethoxysilane, γ- (p-aminophenyl) propyltrimethoxysilane, γ- (p-aminophenyl) ethyltrimethoxysilane, γ- (p-aminophenyl) methyltrimethoxysilane, γ- (p-aminophenyl) propyltriethoxysilane, γ- (p-aminophenyl) ethyltriethoxysilane, γ- (p-aminophenyl) methyltriethoxysilane Silane etc. can be mentioned. Among these, preferred are γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane,
γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane and the like. Particularly preferred are γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane and the like, and one of R is a γ-aminopropyl group. It is a thing. These alkoxysilanes having an amino group can be used alone or in combination of two or more.

The organosilane obtained by hydrolyzing the alkoxysilane having an amino group in the present invention is
An organosilane obtained by adding water to an alkoxysilane or a solution of an alkoxysilane dissolved in a solvent to cause the alkoxy group to undergo a substantially complete hydrolysis reaction.

The organosilane condensate is a product obtained by dehydration condensation reaction of a plurality of organosilanes.

The alkoxysilane having no amino group in the present invention is represented by the general formula R ^a mSi (OR ^b ) 4-m.
An alkoxysilane represented by

R ^a and R ^b in the formula represent hydrogen or an organic group. Examples of the organic group include an alkyl group, an allyl group, an aryl group, an alkenyl group, an alkynyl group, and a fluoroalkyl group. More specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, neohexyl group, vinyl group, allyl group, isopropenyl group , Ethynyl group, 2-propynyl group, 3,3,3-trifluoropropyl group, γ-glycidoxypropyl group, methacryl group,
Examples thereof include γ-methacryloxypropyl group, phenyl group and tolyl group. However, R ^a and R ^b do not contain an amino group.

R ^a and R ^b may be the same or different. The m R ^a 's may be the same or different. The (4-m) OR ^b groups may be the same or different. m is a number from 0 to 3.

[0026] Specific examples of such R ^a m Si (OR ^b) alkoxysilane having no amino group represented by 4-m are tetraethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, Examples thereof include tetramethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and isobutyltrimethoxysilane. Among these, preferred are tetraethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, and particularly preferred are phenyltriethoxysilane,
It is preferable that at least one of R ^a such as phenyltrimethoxysilane is a phenyl group. These alkoxysilanes having no amino group can be used alone or in combination of two or more kinds. Examples of the polycarboxylic acid anhydride in the present invention include tetracarboxylic acid dianhydride, tricarboxylic acid monoanhydride, tetracarboxylic acid monoanhydride, and the like, but tetracarboxylic acid dianhydride is common. Examples of the tetracarboxylic dianhydride may include all known tetracarboxylic dianhydrides. Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3
′, 4′-benzophenone tetracarboxylic acid dianhydride,
2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 1,2,
5,6-naphthalene tetracarboic acid dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, 3,3 ', 4,4'
-Diphenyldimethylmethanetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyldi (trifluoromethyl) methanetetracarboxylic dianhydride, 3,3',
4,4′-diphenylsulfone tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 1,2,4,5-tetracarboxylic acid dianhydride,
3,3 ′, 4,4′-diphenylmethanetetracarboxylic dianhydride, 2,3,4,5-thiophenetetracarboxylic tetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid Examples thereof include, but are not limited to, dianhydride. Among these, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable. Of these, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride is particularly preferable. It is also possible to use an acid anhydride terminated polyamic acid. Examples of the polyamic acid used herein include compounds produced by the reaction of diamine and tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride include the above-mentioned tetracarboxylic acid dianhydride, and examples of the diamine include known diamines. For example, 4,4'-diaminodiphenyl ether, 3,3 '(or 4,4'
′) -Diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, paraphenylenediamine,
4,4'-diaminodiphenylmethane, bis (3-aminopropyl) tetramethyldisiloxane, metaphenylenediamine, 4,4'-diaminodiphenylethane,
1,5-diaminonaphthalene, 3,3'-dimethyl-
4,4'-diaminobiphenyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone,
3,4'-diaminobenzophenone, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, 1,4- Examples thereof include, but are not limited to, bis (4-aminophenoxy) benzene.

The polyvalent carboxylic acid according to claim 6 in the present invention means a carboxylic acid obtained by partially or completely hydrolyzing the above-mentioned acid anhydride.

The reaction ratio of at least one of an alkoxysilane having an amino group, an organosilane obtained by hydrolyzing the alkoxysilane, and a condensate of the organosilane to a polyvalent carboxylic acid anhydride in the present invention is as follows. Although not particularly limited, the alkoxysilane, the organosilane, and the total number of moles of amino groups of at least one of the condensates of the organosilane, and the acid anhydride group of the polyvalent carboxylic acid anhydride is about equimolar. A ratio such that

At least one of an alkoxysilane having an amino group, an organosilane obtained by hydrolyzing the alkoxysilane in the present invention, and a condensate of the organosilane, a polyvalent carboxylic acid anhydride and / or a polyvalent carboxylic acid. The mixing ratio with the acid is not particularly limited, but the total number of moles of the amino group having at least one of alkoxysilane having an amino group, organosilane obtained by hydrolyzing the alkoxysilane, and a condensate of the organosilane. And a polycarboxylic acid anhydride and / or a polycarboxylic acid having an acid anhydride group and a total number of moles of carboxyl groups in the polycarboxylic acid are preferably in a ratio of about equimolar.

Generally, a carboxyl group is formed by reacting a polyvalent carboxylic acid anhydride with an amino group, and the carboxyl group may be modified into a carboxylic acid ester.

A surfactant may be added to the thermosetting resin composition of the present invention for the purpose of improving coatability.
If necessary, a metal chelate compound may be added to the thermosetting resin composition of the present invention in order to enhance the adhesiveness to a substrate such as glass after thermosetting.

The curable composition of the present invention is applied onto a substrate by an inkjet method and then subjected to a curing treatment to form a coating film. Heat treatment is preferable as the curing treatment method, and examples of the heat treatment method include a ventilation oven, a hot plate,
A vacuum oven, a furnace or the like can be used. A ventilation oven or a hot plate is preferable. The heat treatment temperature is preferably 50 to 400 ° C, more preferably 150 to 350 ° C, and further preferably 200.
３００300 ° C. The temperature may be raised rapidly to this heat treatment temperature or may be raised stepwise. The method of raising the temperature stepwise is preferred. The heat treatment time at the maximum heat treatment temperature is preferably 10 minutes to 10 hours, more preferably 30 minutes to 4 hours in the case of a ventilation oven.
In the case of a hot plate, the time is shorter than this, preferably 2 minutes to 2 hours, more preferably 6 minutes to 1 hour. Further, photocuring can be performed by adding a photosensitive component to the thermosetting resin composition.

The coating film thus obtained is used in addition to the protective film and the flattening film provided on the color filter, as well as the protective film of the semiconductor element, the interlayer insulating film, the flattening film, the material for forming the waveguide, and the phase. It can be used as a shifter material, a protective film for various electronic components, and the like.

For example, when it is used as a protective film for a color filter, it is heat-cured according to the present invention on a colored layer on a transparent substrate such as glass and, if necessary, on a light-shielding layer provided between the colored layers. The resin composition is applied and cured to form a transparent protective film.

[0035]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto.

Reference Example 1 136 g (1.0 mol) of methyltrimethoxysilane, 198 g (1.0 mol) of phenyltrimethoxysilane,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (32.2 g, 0.1 mol) was converted to γ-butyrolactone (140 g) and 3-methyl-3-methoxybutanol (42).
It was dissolved in 1 g, and while stirring at 30 ° C., 118 g of distilled water was added and stirred for 2 hours to carry out hydrolysis / condensation.

This solution was heated and stirred at a bath temperature of 105 ° C. for 3 hours to distill off 140 g of alcohol and water produced, and then γ-aminopropylmethyldiethoxysilane 38.
3 g (0.2 mol) was converted to 133 g of γ-butyrolactone,
-Methyl-3-methoxybutanol (355.0 g) was added, and the mixture was heated and stirred at the same temperature for 1 hour, then gradually heated and heated under stirring to obtain a bath temperature of 1 hour.
The mixture was heated and stirred at 35 ° C for 2 hours, and the reaction temperature was set at 125 ° C.
The produced alcohol and 75 g of water were distilled off.

The solution thus obtained was cooled to room temperature and then added with a solution of 0.5 g of silicone surfactant BYK302 (manufactured by BYK-Chemie) in 60.0 g of 3-methyl-3-methoxybutanol. Diluted to obtain a thermosetting resin composition solution.

The solid content concentration of the solution thus obtained was measured by the solvent removal method of heating at 300 ° C. for 30 minutes, and it was 1
It is 8.2% by weight and the viscosity is 17.4 centipoise (2
5 ° C.). 1. The result of measuring the resistance value of this solution
It was 7 × 10 ⁵ Ω · cm. Reference Example 2 13.6 g (0.1 mol) of methyltrimethoxysilane and 19.8 g (0.1 mol) of phenyltrimethoxysilane.
And γ-aminopropylmethyldiethoxysilane
0 g (0.5 mol) of 428.0 g of 3-methyl-3-methoxybutanol and 333.3 g of γ-butyrolactone
28.8 g of distilled water with stirring at 30 ° C.
(1.8 mol) was added. After stirring this solution at 60 ° C. for 4 hours, 80.6 g (0.25 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride was added, and stirring was continued for 2 hours as it was, followed by thermosetting. A resin composition was obtained. The viscosity of this solution was measured by an E-type viscometer and found to be 22.5 centipoise (25 ° C.).

As a result of measuring the resistance value of this solution, 3.7 ×
It was 10 ⁵ Ω · cm.

Reference Example 3 32.23 g (0.10 mol) of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride was added to 3-methyl-
After adding and dissolving to a mixed solution of 100.0 g of 3-methoxybutanol and 100.0 g of γ-butyrolactone,
38.40 g of aminopropylmethyldiethoxysilane
(0.2 mol) in 68.1 g of 3-methyl-3-methoxybutanol was added dropwise over a period of about 10 minutes.
The reaction was carried out at 0 ° C. for 1 hour to obtain a thermosetting resin composition solution. The viscosity of this solution was measured by an E-type viscometer and found to be 17.5 centipoise (25 ° C.). As a result of measuring the resistance value of this solution, it was 2.0 × 10 ⁵ Ω · cm.

Reference Example 4 272.0 g (2.0 mol) of methyltrimethoxysilane and 396.0 g (2.
0 mol), 0.34 g of acetic acid was dissolved in 785.6 g of 3-methyl-3-methoxybutanol, 216 g of distilled water was added with stirring at 30 ° C., and the mixture was heated and stirred for 1 hour to carry out hydrolysis and condensation. Done.

The solution was gradually heated and stirred and the temperature was raised under stirring for 2 hours, and the bath temperature was adjusted to 130 ° C. for 2 hours under heating and stirring to distill off the produced alcohol and 449.1 g of water. The solution is cooled to 80 ° C. and 3-methyl-3-
Methoxybutanol 85.7 g was added to obtain a thermosetting resin composition solution. The solid content concentration of the thus obtained solution was 31.5 wt% as measured by the solvent removal method of heating at 300 ° C. for 30 minutes, and the viscosity was 51 centipoise (25
℃). The result of measuring the resistance value of this solution is 3.0
It was × 10 ⁵ Ω · cm.

Reference Example 5 100 g of the solution obtained in Reference Example 2, 130 g of the solution obtained in Reference Example 4 and 100 g of the solution obtained in Reference Example 4 were mixed to obtain a thermosetting resin composition solution. Results of measuring the resistance of this solution. It was 3.3 × 10 ⁵ Ω · cm.

Example 1 A black paste prepared by dispersing a black pigment in a polyamic acid was spin-coated on non-alkali glass and heated at 50 ° C. for 10 hours.
Min, 90 ° C. for 10 minutes, 110 ° C. for 20 minutes in an air oven to dry and obtain a polyimide precursor colored film having a thickness of 1.6 μm. A positive type photoresist (OFPR-800 manufactured by Tokyo Ohka Co., Ltd.) is applied on this film and applied with 80
A resist film having a thickness of 1 μm was obtained by heating and drying at 20 ° C. for 20 minutes. 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 photoresist and the polyimide precursor were developed at the same time by immersing in a developer containing 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 give a film thickness of 1.2.
A black matrix pattern was obtained with a polyimide colored coating of μm.

Further, with respect to the color pastes of blue, red, and green in which pigments were dispersed in polyamic acid, patterned polyimide colored coating films were sequentially formed by the same process to obtain a color filter.

Next, 30.0 g of the solution obtained in Reference Example 1
60.0 g of γ-butyrolactone was added to 2.7 g of a 2 wt% tetramethylammonium hydroxide aqueous solution to obtain a thermosetting resin composition solution of the present invention. As a result of measuring the resistance value of this solution, it was 5.1 × 10 ³ Ω · cm. This solution was applied onto a desired region of a color filter by a program-controlled continuous type inkjet coating device.

This was pre-dried in a hot air oven at 100 ° C. for 10 minutes and then heat-treated at 280 ° C. for 0.5 hour. As a result, a good transparent protective film having a thickness of 1.1 μm could be formed.

Example 2 To 30.0 g of the solution obtained in Reference Example 2 was added 60.0 g of γ-butyrolactone, 2.2 g of a 2% by weight aqueous solution of tetramethylammonium hydroxide, and the thermosetting resin of the present invention was added. A composition solution was obtained. The resistance value of this solution was measured and found to be 7.1 × 10 ³ Ω · cm. This solution was applied onto a desired region of a color filter by a program-controlled continuous type inkjet coating device.

This was pre-dried in a hot air oven at 100 ° C. for 10 minutes and then heat-treated at 280 ° C. for 0.5 hour. As a result, a good transparent protective film having a thickness of 1.1 μm could be formed.

Example 3 To 30.0 g of the solution obtained in Reference Example 3 was added 60.0 g of γ-butyrolactone and 2.2 g of a 2% by weight aqueous solution of tetramethylammonium hydroxide to prepare a thermosetting resin of the present invention. A composition solution was obtained. As a result of measuring the resistance value of this solution, it was 7.5 × 10 ³ Ω · cm. This solution was applied onto a desired region of a color filter by a program-controlled continuous type inkjet coating device.

This was pre-dried in a hot air oven at 100 ° C. for 10 minutes and then heat-treated at 280 ° C. for 0.5 hour. As a result, a good transparent protective film having a thickness of 1.1 μm could be formed.

Example 4 To 30.0 g of the solution obtained in Reference Example 4 was added 60.0 g of γ-butyrolactone, 2.7 g of a 2% by weight aqueous solution of tetramethylammonium hydroxide, and the thermosetting resin of the present invention was added. A composition solution was obtained. As a result of measuring the resistance value of this solution, it was 4.3 × 10 ³ Ω · cm. This solution was applied onto a desired region of a color filter by a program-controlled continuous type inkjet coating device.
This was pre-dried in a hot air oven at 100 ° C. for 10 minutes and then heat-treated at 280 ° C. for 0.5 hour, resulting in 1.1 μm.
A transparent protective film having a good thickness could be formed into a pattern.

Example 5 To 30.0 g of the solution obtained in Reference Example 5 was added 60.0 g of γ-butyrolactone, 2.7 g of a 2% by weight aqueous solution of tetramethylammonium hydroxide, and the thermosetting resin of the present invention was added. A composition solution was obtained. The resistance value of this solution was measured and found to be 5.2 × 10 ³ Ω · cm. This solution was applied onto a desired region of a color filter by a program-controlled continuous type inkjet coating device.
This was pre-dried in a hot air oven at 100 ° C. for 10 minutes and then heat-treated at 280 ° C. for 0.5 hour, resulting in 1.1 μm.
A transparent protective film having a good thickness could be formed into a pattern.

Comparative Example 1 In Example 1, 30 g of the solution obtained in Reference Example 1 was added.
Using the same solution as in Example 1 except that the tetramethylammonium hydroxide aqueous solution was not added, coating with a program-controlled continuous type inkjet coating apparatus was tried, but the coating could not be performed according to the program. The desired protective film could not be formed by patterning because it was also applied outside the application area.

Comparative Example 2 In 30 g of the solution obtained in Reference Example 2 in Example 2,
Using a solution exactly the same as that of Example 2 except that the tetramethylammonium hydroxide aqueous solution was not added, coating with a program-controlled continuous type inkjet coating apparatus was tried, but the coating could not be performed according to the program. The desired protective film could not be formed by patterning because it was also applied outside the application area.

Comparative Example 3 In Example 3, 30 g of the solution obtained in Reference Example 3 was added,
A completely similar solution to that of Example 3 was used except that the tetramethylammonium hydroxide aqueous solution was not added, and coating with a program-controlled continuous type inkjet coating apparatus was attempted. The desired protective film could not be formed by patterning because it was also applied outside the application area.

Comparative Example 4 In Example 4, 30 g of the solution obtained in Reference Example 4 was added,
Using a solution exactly the same as in Example 4 except that the tetramethylammonium hydroxide aqueous solution was not added, coating with a program-controlled continuous type inkjet coating apparatus was attempted, but the coating could not be performed according to the program. The desired protective film could not be formed by patterning because it was also applied outside the application area.

Comparative Example 5 In Example 5, 30 g of the solution obtained in Reference Example 5 was added,
The same solution as in Example 5 was used, except that γ-butyrolactone and an aqueous tetramethylammonium hydroxide solution were not added, and coating with a program-controlled continuous type inkjet coating apparatus was attempted. This was not possible, and it was applied outside the desired application area, and the desired protective film could not be patterned.

[0061]

EFFECT OF THE INVENTION In a color filter in which a colored film is formed on a transparent substrate, a method of forming a protective film on the colored film by a continuous ink jet method is used to transparently protect only a desired region of a color filter screen. A color filter having a patterned film can be easily obtained.

Claims (9)

[Claims] 1. A thermosetting resin composition comprising a solvent component and a resin component, containing an ammonium compound represented by the formula (1) and having a resistance value of less than 1 × 10 ⁵ Ω · cm. A thermosetting resin composition for forming a transparent protective film. R ^* ₄ N ⁺ X ⁻ (1) (N is a nitrogen atom, R ^* is an organic group or a hydrogen atom, and X ⁻ is an anion.) 2. The thermosetting resin composition for forming a transparent protective film according to claim 1, which has a resistance value of less than 1 × 10 ⁴ Ω · cm. 3. The thermosetting resin composition for forming a transparent protective film according to claim 1, wherein X ⁻ is a hydroxide ion. 4. The thermosetting resin composition for forming a transparent protective film according to claim 1, wherein R ^* is a methyl group or an ethyl group. 5. The resin component reacts at least one of an alkoxysilane having an amino group, an organosilane obtained by hydrolyzing the alkoxysilane, and a condensate of the organosilane with a polyvalent carboxylic acid anhydride. The thermosetting resin composition for forming a transparent protective film according to any one of claims 1 to 4, which contains a compound obtained by the above. 6. A resin component comprising at least one of an alkoxysilane having an amino group, an organosilane obtained by hydrolyzing the alkoxysilane, and a condensate of the organosilane, and a polyvalent carboxylic anhydride or / and The thermosetting resin composition for forming a transparent protective film according to claim 1, which contains a mixture with a polyvalent carboxylic acid. 7. The resin component further contains at least one of an alkoxysilane having no amino group, an organosilane obtained by hydrolyzing the alkoxysilane, and a condensate of the organosilane. Item 7. A thermosetting resin composition for forming a transparent protective film according to item 5 or 6. 8. A color filter in which at least a colored layer and a protective film are provided in this order on a transparent substrate, wherein the protective film comprises the thermosetting resin composition for forming a transparent protective film according to any one of claims 1 to 7. A color filter characterized by being applied and cured. 9. A color filter in which at least a colored layer and a protective film are provided in this order on a transparent substrate, wherein the protective film comprises the thermosetting resin composition for forming a transparent protective film according to any one of claims 1 to 7. A color filter characterized by being applied and cured on a specific area on a substrate.