JPH1087769A - Resin composition, its film and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition, film and its cured product developable with water, a dilute alkaline aqueous solution or an organic solvent, giving excellent pattern accuracy, leaving little organic residue after incineration and useful e.g. as a color filter having high adhesivity. SOLUTION: This resin composition contains (A) a resin containing an unsaturated group and produced by reacting (a) an epoxy resin having >=2 epoxy groups in one molecule with (b) a compound having one unsaturated double bond and one carboxyl group in one molecule and optionally (c) a saturated monocarboxylic acid and optionally reacting the resultant epoxy (meth)acrylate with (d) a polybasic acid anhydride, (B) a diluent, (C) a photo-polymerization initiator, (D) an inorganic pigment and (E) glass powder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is suitably used in a process of manufacturing a color filter or the like used for a plasma display or a fluorescent display tube, etc., at 400 to 1000.degree.
The present invention relates to a resin composition that forms a color filter or the like by baking, a film thereof, a cured product thereof, and a fired molded product.

[0002]

2. Description of the Related Art In recent years, in a self-luminous display such as a plasma display, a system using a color filter has been studied in order to optimize the luminous characteristics.
Since this color filter may be exposed to the discharge space or may be heated by the discharge, it must be made of an inorganic material having high robustness. Thus, a color filter is formed by printing a paste made of an inorganic pigment and a low-melting glass by screen printing or the like and baking the paste, but it cannot cope with high density and fine line patterning. Therefore, a photo process using a photosensitive resin has been studied, but it has been difficult to achieve high definition and high sensitivity.

[0003]

The resin composition of the present invention improves the above-mentioned disadvantages, enables formation of a fine pattern with high sensitivity, cures with ultraviolet rays, and develops with water or an aqueous alkali solution to obtain a good color. Provided are a resin composition for forming a filter and the like and a cured product thereof.

[0004]

The present invention relates to [1] an epoxy resin (a) having at least two epoxy groups in a molecule and one unsaturated double bond and one carboxyl group in one molecule. (Meth) which is a reaction product of the compound (b) having the compound and a saturated monocarboxylic acid (c) as an optional component
Unsaturated group-containing resin (A) obtained by reacting acrylate with polybasic acid anhydride (d) if necessary, diluent (B), photopolymerization initiator (C), inorganic pigment (D) and glass powder ( E) a resin composition, [2] a resin composition according to the above [1] for a color filter, and [3] a film comprising the resin composition according to the above [1] and [2]. ,
[4] A cured product of the resin composition according to [1], [2] or [3], [5] A resistor, a conductor, a phosphor and a partition wall obtained by firing the cured product according to [4]. , Concerning.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The resin (A) used in the present invention comprises a compound (a) having two or more epoxy groups in one molecule, a compound (b) having one unsaturated double bond and one carboxyl group in one molecule, and Is a resin obtained by reacting a saturated carboxylic acid (c) according to the above, and optionally a polybasic anhydride (d).

Specific examples of the compound (a) having two or more epoxy groups in one molecule include bisphenol A type epoxy resin (for example, Epicoat 828, Epicoat 1001, manufactured by Yuka Shell Epoxy Co., Ltd.) Epicoat 1002, Epicoat 1004, etc.), an epoxy resin obtained by reacting an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (eg,
Nippon Kayaku Co., Ltd., NER-1302, epoxy equivalent 3
23, softening point 76 ° C), bisphenol F type resin (eg,
Yuka Shell Epoxy Co., Ltd., Epicoat 807, EP
-4001, EP-4002, EP-4004, etc.), an epoxy resin obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (eg, NER-7406, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 350, Softening point 66 ° C.), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg, Yuka Shell Epoxy Co., Ltd., YX-4000), phenol novolak type epoxy resin (eg, Nippon Kayaku Co., Ltd.), E
EP-201, manufactured by Yuka Shell Epoxy Co., Ltd., EP-
152, EP-154, manufactured by Dow Chemical Co., Ltd., DEN
-438), cresol novolak type epoxy resin (eg, Nippon Kayaku Co., Ltd., EOCN-102S, EOCN
-1020, EOCN-104S), triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd., TEPIC), trisphenolmethane epoxy resin (Nippon Kayaku Co., Ltd.)
, EPPN-501, EPN-502, EPPN-5
03), fluorene epoxy resin (eg, Nippon Steel Chemical Co., Ltd., Cardo epoxy resin, ESF-300), alicyclic epoxy resin (Daicel Chemical Industries, Ltd., Celloxide 2021P, Celloxide EHPE) and the like. Can be

[0007] Another example of (a) is a copolymerizable epoxy resin. As a copolymer type epoxy resin,
For example, a compound having one epoxy group and one ethylenically unsaturated group in one molecule such as glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, and vinylcyclohexene oxide, and containing other monofunctional ethylenically unsaturated groups Compounds (eg, methyl (meth) acrylate, ethyl (meth) acrylate,
Butyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono ( Meth) acrylate, general formula (1)

[0008]

Embedded image

(Wherein R ₁ is hydrogen or an ethyl group, R ₂ is hydrogen or a C1-C6 alkyl group, and n is 2-23
Is an integer, and copolymers obtained by reacting one or two or more selected from the group consisting of: Specifically, Nippon Oil & Fats Co., Ltd., CP-15, CP-30, CP-50,
CP-20SA, CP-510SA, CP-50S, C
P-50M, CP-20MA, etc.). Examples of the compound of the formula (1) include polyethylene glycol mono (meth) acrylate such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate, and methoxydiethylene glycol mono (meth) acrylate. Alkoxy polyethylene glycol (meth) acrylates such as acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate;

The molecular weight of the copolymer type epoxy resin is about 1
000 to 200,000 is preferred. The amount of the compound having one epoxy group and one ethylenically unsaturated group in one molecule is preferably from 10 to 70% by weight, particularly preferably from 10 to 70% by weight, based on the total amount of unsaturated monomers used in the copolymerizable epoxy resin. Is from 20 to 50% by weight.

When a copolymerizable epoxy resin which can be developed with water is obtained, glycerin mono (meth) acrylate and / or the compound of the general formula (1) is added to the total amount of unsaturated monomers used in the polymer. On the other hand, it is desirable to add 30% by weight or more, particularly preferably 50% by weight or more.

The copolymerizable epoxy resin can be obtained by a known polymerization method, for example, solution polymerization, emulsion polymerization or the like. To explain the case of using solution polymerization,
The ethylenically unsaturated monomer mixture is added to a polymerization initiator in an applicable organic solvent, and is preferably added under a nitrogen stream under a nitrogen stream.
The polymerization is carried out by heating and stirring at 00 ° C. Examples of the organic solvent include ethanol, propanol,
Isopropanol, butanol, isobutanol, 2-
Alcohols such as butanol, hexanol and ethylene glycol, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve,
Carbitols such as carbitol and butyl carbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol Examples thereof include acetic esters such as monomethyl acetate, lactic esters such as ethyl lactate and butyl lactate, and dialkyl glycol ethers. These organic solvents can be used alone or in combination.

As the polymerization initiator, for example, peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile can be used.

The compound (b) having one unsaturated double bond and one carboxyl group in one molecule includes (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate (for example,
Acid anhydrides of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compounds (for example, succinic anhydride, maleic anhydride) Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.).

Specific examples of the saturated monocarboxylic acid (c) include, for example, acetic acid, propionic acid, pivalic acid, hydroxypivalic acid, dimethylolpropionic acid, benzoic acid and hydroxybenzoic acid.

It is preferable that 0.5 to 1.1 equivalents of the compound (b) and the saturated monocarboxylic acid (c) as an optional component are reacted with 1 equivalent of the epoxy group of the epoxy resin (a). Also, a reaction solvent may be used if necessary,
For example, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, alcohols such as ethylene glycol, methyl ethyl ketone, ketones such as cyclohexanone, toluene, aromatic hydrocarbons such as xylene, cellosolve,
Cellosolves such as butyl cellosolve, carbitols such as carbitol and butyl carbitol, propylene glycol alkyl ethers such as propylene glycol methyl ether, polypropylene pyrene glycol alkyl ethers such as dipropylene glycol methyl ether, ethyl acetate, butyl acetate And acetates such as cellosolve acetate and propylene glycol monomethyl acetate, lactates such as ethyl lactate and butyl lactate, and dialkyl glycol ethers. These organic solvents can be used alone or as a mixture.

In order to promote the reaction, a basic compound such as triphenylphosphine, triphenylstibine, triethylamine, triethanolamine, tetramethylammonium chloride, benzyltriethylammonium chloride or the like is added to the reaction mixture as a reaction catalyst in an amount of 0.1 to 0.1%. 1
% Is preferably added. During the reaction, it is preferable to add a polymerization inhibitor (for example, methoxyphenol, methylhydroquinone, hydroquinone, phenothiazine, etc.) in the reaction solution in an amount of 0.05 to 0.5% in order to prevent polymerization.
The reaction temperature is preferably 90 to 150 ° C, and the reaction time is preferably 5 to 40 hours.

If necessary, an acid anhydride (d) of a polycarboxylic acid compound (for example, succinic anhydride, maleic anhydride, anhydride, etc.) is added to one equivalent of the hydroxyl group of the epoxy (meth) acrylate thus obtained. Phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) can be reacted preferably in an amount of from 0.2 to 1.0 equivalent of an anhydride group.
The reaction temperature is preferably 90 to 150 ° C, and the reaction time is preferably 3 to 30 hours.

In the present invention, a diluent (B) is used.
Specific examples of the component (B) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloyl Acid anhydride of morpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compound (Eg, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) half ester, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, Methylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycene polypropoxytri (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopyrene glycol hydroxybivalate (for example, KAY manufactured by Nippon Kayaku Co., Ltd.
ARAD HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono or polyglycidyl Compounds (for example, butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Epoxy which is a reaction product of (meth) acrylic acid with hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc. Reactive diluents (B-1) such as meth) acrylates, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers,
Diethylene glycol monoalkyl ether acetates, ethylene glycol monoaryl ethers, polyethylene glycol monoaryl ethers, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetates, esters such as butyl acetate,
Toluene, xylene, aromatic hydrocarbons such as benzyl alcohol, propylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, ethylene carbonate, propylene carbonate,
Organic solvents (B-2) such as γ-butyrolactone and solvent naphtha can be exemplified. The diluents may be used alone or as a mixture of two or more.

Specific examples of the photopolymerization initiator (C) include, for example, 2,4-diethylthioxanthone, 2-chlorocutixanthone, isopropylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propane-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide, Michler's ketone, benzyldimethyl ketal, and 2-ethylanthraquinone. Further, a photopolymerization accelerator (for example, amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester) as an accelerator of the photopolymerization initiator (B) is used in combination. You can also.

Specific examples of the inorganic pigment (D) include zinc white, lead white, basic lead sulfate, lead sulfate, lipoton, zinc sulfide, titanium oxide, antimony oxide, and carbon dioxide having a particle size of preferably 10 μm or less. Black, acetylene black, lamp black, bone black, graphite, iron black, mineral black, cyanine black, graphite, zinc yellow, barium chromate, cadmium yellow, yellow iron oxide, loess, titanium yellow, lead cyanamide, calcium leadate , Red mouth yellow lead, chrome vermillion, iron oxide, amber, permanent brown FG, para brown, red iron, lead red, silver vermilion, cadmium red, cadmium mercury red,
Antimony vermilion, cobalt purple, manganese purple, ultramarine, navy blue,
Cobalt blue, Cerulean blue, Kuresu, chrome green, zinc green, chromium oxide, viridian, emerald green, cobalt green, zinc sulfide, zinc silicate, zinc cadmium, calcium sulfide, strontium sulfide, calcium tungstate, etc. . These inorganic pigments may be used in combination of two or more.

The glass powder (E) has an average particle size of 20.
Glass having a low melting point of not more than μm is preferred. These glass powders may be surface-treated with a coupling agent or a polymer.

The resin composition of the present invention comprises (A), (B),
It can be prepared by dissolving, mixing and kneading the components (C), (D) and (E). In the resin composition of the present invention, the use ratio of each component can be as follows (% is% by weight). The total usage of (A) + (B-1) + (C) is preferably 5 to 60% based on the composition,
Particularly preferably, it is 10 to 50%. (D) + (E) component is preferably 40 to 95%, particularly preferably 50 to 90% in the composition, and the ratio between (D) and (E) is
(D) is 5 to 95%, and (E) is 5 to 95%.
The preferred use amount of each component in the total amount of (A) + (B-1) + (C) is that the use amount of component (A) is 30 to
90%, the amount of the component (B-1) used is 5 to 65%,
The amount of the component (C) used is 5 to 30%. The amount of the organic solvent (B-2) can be used in any ratio for the purpose of adjusting the viscosity and the like suitable for using the composition of the present invention.

In the resin composition of the present invention, a leveling agent, an antifoaming agent, a coupling agent, a polymerization inhibitor, a wax, etc. may be used as long as the performance is not impaired.

As described above, the resin composition of the present invention comprises a composition for a resistor, a resin composition for a phosphor, a resin composition for a partition,
It can be used as a resin composition for a conductive circuit, and these are applied to the entire surface of various substrates (for example, glass, ceramic, metal, and the like) by a method such as screen printing, curtain flow coating, or spray coating. The coating film thickness is preferably from 0.1 μm to 50 μm, and particularly preferably from 1 μm to 10 μm. After the application, if necessary, pre-baking is performed at about 50 to 250 ° C. with far infrared rays or warm air to remove the organic solvent, and then the film is exposed to ultraviolet rays using a negative mask that allows only the portions to be patterned to pass ultraviolet rays. The exposure amount of ultraviolet rays is preferably from 10 to 10,000 mJ / cm ² . Next, development is performed by means such as spraying with water or a dilute alkaline aqueous solution at a liquid temperature of 10 to 60 ° C., and then, for example,
It is baked at 400 to 1000 ° C. for 1 to 24 hours to form a pattern.

When used as a film, the resin composition of the present invention is applied to a release film or the like by using, for example, a wire bar system, a dipping system, a spin coating system, a gravure system, a doctor blade system or the like. It is dried at 50 to 250 ° C. by far-infrared rays or warm air as needed, and a release film or the like is attached as needed. When using, peel off the release film and transfer it to the substrate,
A pattern is formed by exposure, development, and baking as described above.

[0027]

The present invention will be described below with reference to Examples 1 to 9. In the examples, “parts” means “parts by weight”. According to the compositions shown in Tables 1 and 2, resin compositions for color filters were prepared. The resulting resin composition was applied to the entire surface of a glass substrate using a guide at a film thickness of 10 μm (dry film thickness), prebaked at 80 ° C. for 30 minutes, and then a negative film (line / space = 150 μm / 150 μm) ) Was irradiated with 1500 mJ / cm ² by an ultra-high pressure mercury lamp, and the unexposed portion was developed with a developing solution (40 ° C.) at a spray pressure of 2 kg / cm ² for 2 minutes. After the development, baking was performed at 500 ° C. for 1 hour in the air to form partition walls and a phosphor pattern. The residual resin content in the pattern, the developability, the state of the pattern after development, and the adhesion to the glass substrate after firing were evaluated.

Synthesis Example 1 (Synthesis example of reactant A) A trisphenolmethane-type epoxy resin (Nippon Kayaku Co., Ltd., EPPN-503, epoxy equivalent 200, (Softening point 83 ° C) 200 parts, acrylic acid 72
, 0.2 parts of methylhydroquinone and 169.1 parts of propylene glycol monomethyl ether acetate, and the mixture was heated to 90 ° C. and dissolved. Then, the mixture was cooled to 60 ° C. and charged with 1.2 parts of triphenylphosphine.
After reacting for 32 hours, tetrahydrophthalic anhydride 1
12.6 parts were charged and reacted at 95 ° C. for 15 hours to obtain an unsaturated group-containing polycarboxylic acid resin having a solid content acid value (mg KOH / g) of 100.

Synthesis Example 2 (Synthesis example of reactant (A)) A round-bottomed flask equipped with a stirring device and a condenser was charged with a copolymerization type epoxy resin (manufactured by NOF Corporation, Blenmer CP-50M, epoxy equivalent 31).
0, average molecular weight 6000) 310 parts, acrylic acid 72
, 0.3 parts of methylhydroquinone and 244.5 parts of propylene glycol monomethyl ether acetate, and the mixture was heated to 60 ° C. and dissolved. Then, the mixture was cooled to 60 ° C., and 1.8 parts of triphenylphosphine was charged.
After reacting for 32 hours at 70 ° C., 70 parts of succinic anhydride was charged and reacted at 95 ° C. for 15 hours to obtain a solid acid value (mg KO).
H / g) 80 unsaturated group-containing polycarboxylic acid resin was obtained.

(Synthesis Example of Reactant (A)) Synthesis Example 3 70 parts of glycerol methacrylate, 30 parts of glycidyl methacrylate, 100 parts of carbitol acetate, and 3 parts of benzoyl peroxide were added, and heated at 75 ° C. under a nitrogen stream. Polymerization was carried out for 5 hours to obtain a 50% polymer solution. Next, 300 parts of this 50% polymer solution, 22.8 parts of acrylic acid, and 0.16 of methylhydroquinone were added.
, 0.9 part of triphenylphosphine and 250 parts of carbitol acetate were mixed and dissolved, and reacted at 95 ° C. for 32 hours to obtain a reaction product solution. The average molecular weight of the reactants is about 1
It was 20,000.

Synthesis Example 4 50 parts of tetraethylene glycol monomethacrylate,
25 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 2 parts of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream, polymerized at 75 ° C. for 5 hours, and a 50% polymer solution was obtained. Obtained. Then, this 50%
300 parts of polymer solution, 19 parts of acrylic acid, 0.16 part of methylhydroquinone, 0.9 parts of triphenylphosphine
Parts, 250 parts of carbitol acetate were mixed and dissolved,
The reaction was performed at 95 ° C. for 32 hours to obtain a reaction solution. The average molecular weight of the reaction was about 80,000.

Synthesis Example 5 70 parts of methoxytetraethylene glycol monomethacrylate, 30 parts of glycidyl methacrylate, 100 parts of carbitol acetate and 3 parts of benzoyl peroxide were added, and the mixture was heated under a stream of nitrogen and polymerized at 75 ° C. for 5 hours. A 50% polymer solution was obtained. Then, 300 parts of this 50% polymer solution, 22.8 parts of acrylic acid, 0.16 part of methylhydroquinone, 0.9 part of triphenylphosphine
Parts, 250 parts of carbitol acetate were mixed and dissolved,
The reaction was performed at 95 ° C. for 32 hours to obtain a reaction solution. The average molecular weight of the reaction product was about 170,000.

[0033]

Table 1 Example 1 Example 1 2 3 4 Polymer obtained in Synthesis Example 1 15.4 15.4 7.7 Polymer obtained in Synthesis Example 2 15.4 7.7 KAYARAD PEG400DA * 175 5 KAYARAD DPHA * 22 2 KAYARAD DPCA-60 * 3 27 KAYACURE DETX-S * 42 2 22 KAYACURE EPA * 5 222 2 Cadmium red 20 20 Ultramarine 20 20 Low melting glass 20 20 20 20 20 Propylene glycol monomethyl ether acetate 15 15 15 15 Residual organic matter (wt% ) 0.1 0.1 0.05 0.05 Developability (1% aqueous solution of sodium carbonate) ○ ○ ○ ○ State of pattern after development ○ ○ ○ ○ Adhesion ○ ○ ○ ○

[0034]

Table 2 Example 2 Example 5 6 7 8 Polymer obtained in Synthesis Example 3 22.7 17.0 Polymer obtained in Synthesis Example 4 22.8 Polymer obtained in Synthesis Example 5 20.0 Diacrylate of tetraethylene glycol diglycidyl ether 221118 KAYARAD PEG400DA 75 KAYARAD DPHA 22 KAYACURE DETX-S 222 2 KAYACURE EPA 222 2 Cadmium Red 20 20 Ultramarine 20 20 Low melting point glass 20 20 20 20 propylene glycol monomethyl ether 20 propylene glycol monomethyl ether 20 propylene glycol monomethyl ether Organic matter (wt%) 0.2 0.3 0.1 0.15 Developability (water) ○ ○ ○ ○ State of pattern after development ○ ○ ○ ○ Adhesion ○ ○ ○ ○

Note * 1 KAYARAD PEG400DA: polyethylene glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.) * 2 KAYARAD DPHA: dipentaerythritol penta and hexaacrylate (Nippon Kayaku Co., Ltd.)
* 3 KAYARAD DPCA-60: caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) * 4 KAYACURE DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) * 5 KAYACURE EPA: manufactured by Nippon Kayaku Co., Ltd.
p-Dimethylaminobenzoic acid ethyl ester

Example 9 The resin composition of Example 1 was applied to a release film so that the film thickness after drying was 30 μm, and dried at 80 ° C. for 30 minutes to obtain a film. This film was transferred to a glass substrate and brought into contact with a negative film.
m ² irradiation, and then the unexposed portion was developed with a 1% aqueous sodium carbonate solution (40 ° C.) at a spray pressure of 2 kg / cm ² for 2 minutes. After the development, baking was performed at 500 ° C. for 1 hour in the air to form a partition wall pattern. Resin content in pattern, developability,
The state of the pattern after development and the adhesion to the glass substrate after firing were all す べ て.

(Residual organic content): The weight loss after heating and baking at 500 ° C. for 60 minutes was measured. (Developability): Developed with an organic solvent-based developer at a liquid temperature of 40 ° C. and a spray pressure of 2 kg / cm ² for 2 minutes. And evaluated as follows: ○: Completely developed △: Slight residue ×: Undeveloped part-: Part or all of the pattern Peeled off (state of pattern after development): ○ ・ ・ ・ ・ The pattern is maintained accurately △ ・ ・ ・ ・ The width of the pattern is narrow × ・ ・ ・ ・ Part of the pattern part or All peeled off (adhesion): Cellophane tape peeling test was performed ○ ・ ・ ・ ・ No peeling at all △ ・ ・ ・ ・ Partially peeled off × ・ ・ ・ ・ Many peeled parts

As is clear from the results of Examples 1 to 9 and Comparative Example, the resin composition, film and cured product thereof of the present invention have excellent developability, good pattern accuracy after development,
Low residual organic matter after firing and excellent adhesion.

[0039]

The resin composition and film of the present invention are excellent in developability in forming a color filter by selectively exposing to ultraviolet light through a film on which a pattern is formed, and developing an unexposed portion. The pattern accuracy is good, the organic matter remains little even when fired at a low temperature, and the adhesion is excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01J 11/00 H01J 11/00 Z // C08L 63:00

Claims (5)

[Claims] 1. An epoxy resin (a) having at least two epoxy groups in a molecule, a compound (b) having one unsaturated double bond and one carboxyl group in one molecule, and a saturated monoamine as an optional component. An unsaturated group-containing resin (A) obtained by reacting an epoxy (meth) acrylate that is a reaction product with a carboxylic acid (c) and, if necessary, a polybasic anhydride (d);
A resin composition comprising a diluent (B), a photopolymerization initiator (C), an inorganic pigment (D), and a glass powder (E). 2. The resin composition according to claim 1, which is used for a color filter. 3. A film comprising the resin composition according to claim 1. 4. A cured product of the resin composition according to claim 1, 2 or 3. 5. A color filter obtained by baking the cured product according to claim 4.