JPH1048815A - Resin composition, its film and its cured body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a high sensitivity fine pattern such as a resistor pattern or a phosphor pattern by development with water, an aq. alkali soln. or an org. solvent after curing with UV by using a photopolymerizable resinous compd. and/or a nonreactive resin, a diluent, a photopolymn. initiator and metal powder. SOLUTION: This resin compsn. contains a photopolymerizable resinous compd. (A) and/or a nonreactive resin (A'), a diluent (B), a photopolymn. initiator (C) and one or more kinds (F) of powders selected from among metal powder having ethylenic unsatd. bonds on the surface, metal oxide powder and glass powder and can be developed with water, an aq. alkali soln. or an org solvent. The resinous compd. is a resin (A) obtd. by allowing a compd. having two or more epoxy groups in one molecule to react with a compd. having one unsatd. double bond and one carboxyl group in one molecule and allowing the resultant reactional product to react further with a polybasic acid anhydride. The nonreactive resin (A') is, e.g. polyethylene glycol or polyester as a reactional product of polyethylene glycol with a polybasic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitably used in a process of manufacturing a resistor pattern, a conductor circuit pattern or a phosphor pattern or a partition used for a plasma display, a fluorescent display tube, and an electronic component. A resin composition that forms a good resistor pattern, a circuit pattern having excellent conductivity, a phosphor pattern, a partition wall, and the like for stably flowing an electric current by baking at 400 to 1000 ° C. after development with an organic solvent. , A film thereof, a cured product thereof, and a fired product.

[0002]

2. Description of the Related Art Conventionally, a resistor, a phosphor and a partition for a plasma display, or a conductor for a circuit are made of a resistor paste (a resistor in the form of a paste), a phosphor paste (a phosphor paste). Pattern printing by screen printing or the like, followed by baking, followed by baking paste (partially formed), partition paste (paste of partition material) and conductor paste (paste of conductive material such as copper powder and silver powder). Are known to form a resistor pattern, a phosphor pattern, a partition pattern, or a conductor circuit pattern. It cannot respond to density and fine line patterning. Therefore,
Although a photo process using a photosensitive resin has been studied, it has been difficult to increase the sensitivity.

[0003]

The resin composition of the present invention improves the above-mentioned drawbacks, enables formation of a fine pattern with high sensitivity, is cured with ultraviolet rays, and is developed with water, an aqueous alkali solution or an organic solvent, Provided is a resin composition for forming a favorable resistor pattern, phosphor pattern, partition pattern or conductive circuit pattern, and a cured product thereof.

[0004]

According to the present invention, there is provided [1] a photopolymerizable resin compound (A) and / or a non-reactive resin (A '), a diluent (B), and a photopolymerization initiator (C). And one or more selected from metal powder, metal oxide powder or glass powder having an ethylenically unsaturated bond on the surface (F)
A resin composition which can be developed with water, an aqueous alkaline solution or an organic solvent, [2] a photopolymerizable resin compound (A)
And / or a non-reactive resin (A ′), a diluent (B), a photopolymerization initiator (C), an ultraviolet absorber (D) and / or a colorant (E), and having an ethylenically unsaturated bond on the surface. A resin composition containing one or more (F) selected from metal powder, metal oxide powder or glass powder and developable with water, an aqueous alkaline solution or an organic solvent; [3] resistor pattern The resin composition according to the above [1] and [2], for a conductor pattern, a phosphor pattern or a partition pattern; [4] a film comprising the resin composition according to the above [1], [2] and [3] [5] The above [1], [2], [3] and [4]
[6] A cured product of the resin composition described above, [6] a resistor, a conductor, a phosphor, and a partition wall obtained by baking the cured product of [5].

[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 is obtained by reacting a compound having two or more epoxy groups in one molecule with a compound having one unsaturated double bond and one carboxyl group in one molecule. It is a resin obtained by reacting polybasic acid anhydride (c), and specific examples thereof include Japanese Patent Application No. 7-259528.
(Meth) acrylates of aliphatic glycidyl ethers described above, unsaturated group-containing polycarboxylic acid resins described in Japanese Patent Application No. 7-288194, Japanese Patent Application Nos. 7-314890 and 8-1.
9283, Japanese Patent Application Nos. 8-19284 and 8-330.
99, a poly (meth) acrylate resin, and the like.

The resin (A) will be described more specifically. Compound (a) having two or more epoxy groups in one molecule
As a specific example, for example, bisphenol A type epoxy resin (for example, manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, Epicoat 1001, Epicoat 100)
2, 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 323, softening point 7
6 ° C.), bisphenol F type resin (eg, manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 807, EP-4001, E
P-4002, EP-4004, etc.), bisphenol F
Resin obtained by the reaction between alcoholic hydroxyl group of epi-type epoxy resin and epichlorohydrin (eg, NER-7406, Nippon Kayaku Co., Ltd., epoxy equivalent 350, softening point 66 ° C.), bisphenol S-type epoxy resin, biphenyl glycidyl ether (Eg, YX-4000 manufactured by Yuka Shell Epoxy Co., Ltd.), phenol novolak type epoxy resin (eg, EPPN-20 manufactured by Nippon Kayaku Co., Ltd.)
1. 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, E
OCN-104S), triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd., TEPIC), trisphenolmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EPPN-
501, EPN-502, EPPN-503), fluorene epoxy resin (eg, Nippon Steel Chemical Co., Ltd., cardo epoxy resin, ESF-300), alicyclic epoxy resin (Daicel Chemical Industry Co., Ltd., celloxide) 2021
P, celloxide EHPE) and the like.

[0007] Another example of (a) is a copolymerizable epoxy resin. As a copolymer type epoxy resin,
For example, glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide, and other monofunctional ethylenically unsaturated group-containing 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. Glycidyl (meta)
The use amount of the acrylate is preferably from 10 to 70% by weight, particularly preferably from 20 to 50% by weight, based on the total amount of unsaturated monomers used in the copolymerizable epoxy resin.

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.

The non-reactive resin (A ') used in the present invention comprises:
For example, polyethylene glycol, polyester which is a reaction product of polyethylene glycol and polybasic acid or its anhydride, acrylic polymer, cellulose and the like are exemplified,
Preferably, a water-soluble polyether and / or polyester compound described in JP-A-7-259526,
Examples thereof include rosin and / or phenolic resin containing a carboxyl group described in 288193, a water-soluble polymer described in JP-A-7-314888, and partially saponified polyvinyl acetate described in JP-A-7-314889.

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.

Examples of the ultraviolet absorber (D) include benzotriazole derivatives, benzophenone derivatives, salicylic acid derivatives, and cyanoacrylate derivatives. As the benzotriazole derivative, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2
-Hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-
tert-butylphenyl) benzotriazole, 2-
(2-hydroxy-3-tert-butyl-5-methyl) benzotriazole, 2- (2-hydroxy-3,
5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-
tert-amylphenyl) benzotriazole, 2-
(2-hydroxy-4-octoxyphenyl) benzotriazole, 2- {2-hydroxy-3- (3,4,
5,6-tetrahydrophthalimidomethyl) -5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-nonylphenyl) benzotriazole, 2- (2-hydroxy-5'-methacryloxyethylphenyl) ) As benzophenone derivatives such as -2H-benzotriazole and copolymers thereof, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4- Dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4 '
-Salicylic acid derivatives such as -dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfobenzone include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and 2-ethylhexyl salicylate. And cyanoacrylate derivatives such as homomenthyl salicylate include 2
-Ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate and the like.

Examples of the colorant (E) include dyes and pigments. Examples of the dye include natural dyes and synthetic dyes.Examples of natural dyes include animal dyes such as ancient purple and cochineal, plant dyes such as eye and madder, and mineral dyes such as mineral khaki.Synthetic dyes include nitroso dyes.
Nitro dye, azo dye, stilbene dye, pyrazolone dye, triphenylmethane dye, xanthene dye, acridine dye, quinoline dye, thiazole dye, quinone imine dye, azine dye, oxazine dye, thiazine dye,
Examples include triazine dyes, sulfur dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes and oxidation dyes, and more specifically, Kayaset Flavin FN,
Kaya set Flavin FG, Kaya set yellow
SF-G, Kayaset Orange SF-R, Kayaset Red SF-4G, Kayaset Red SF-
B, Kaya Set Blue FR, Kaya Set Yellow 2G, Kaya Set Yellow GN, Kaya Set Orange G, Kaya Set Red G, Kaya Set Red 130, Kaya Set Red B, Kaya Set Blue N, Kaya Set Black G, Kaya Set Black B, Kaya Set Black AN, Kaya Set Green AB, Kayaset Blue A-
D, Kayaset Yellow AG, Kayaset Orange AN, Kayaset Red AG, Kayaset Red A-2G, Kayaset Red A-BR,
Kayaset Violet AR, Kayaset Blue A-2R, Kayaset Yellow EG, Kayaset Yellow E-AR, Kayaset Red EC
G, Kayaset Red E-BG, Kayaset Blue ARC, Kayalite B, Kayalite OS, and Kayalite OSN (all manufactured by Nippon Kayaku Co., Ltd.). As pigments, zinc white, lead white, basic lead sulfate, lead sulfate, lipotone, zinc sulfide, titanium oxide, antimony oxide, carbon black, acetylene black,
Lamp black, bone black, graphite, iron black, mineral black, aniline black, cyanine black, graphite, zinc yellow, barium chromate, cadmium yellow,
Yellow iron oxide, loess, titanium yellow, lead cyanamide, calcium lead acid, naphthol yellow S, Hansa yellow 10G,
Hansa Yellow 5G, Hansa Yellow 3G, Hansa Yellow G, Hansa Yellow GR, Hansa Yellow A, Hansa Yellow RN, Hansa Yellow R, Pigment Yellow L, Benzidine Yellow, Benzidine Yellow G, Benzidine Yellow G
R, Permanent Erone CG, Balken Fast Yellow 5G, Tartrazine Lake, Quinoline Yellow Lake,
Anslagen Yellow 6GL, Permanent Yellow FG
L, Permanent yellow H10G, Permanent yellow HR, Anthrapyridine yellow, Red lead graphite, Chrome vermillion, Sudan I, Permanent orange, Resole fast orange 3GL, Permanent orange GT
R, Hansa Yellow 3R, Vulcan Fast Orango G
G, Benzidine Orange G, Persian Orange, Indanthrene Brilliant Orange RK, Indanthrene Brilliant Orange GR, Iron Oxide, Amber, Permanent Brown FG, Para Brown, Bengala, Lead Tan,
Silver Vermilion, Cadmium Red, Cadmium Mercury Red, Antimony Vermilion, Permanent Red 4R, Para Red, Fire Red, Parachloroorthoaniline Red, Risole Fast Scarlet G, Brilliant Fast Scarlet, Yoseki, Brilliant Carmine B
S, permanent red F2R, permanent red F
4R, Permanent Red FRL, Permanent Red FRLL, Permanent Red F4RH, Vulcan Fast Rubin B, Vulcan Fast Pink G, Light Fast Red Toner R, Permanent Carmine FB, Pyrazolone Red, Risor Red, Lake Red C, Lake Red D, Ansosine B , Brilliant Scarlet G, Lisor Rubin GK, Permanent Red F5
R, Brilliant Toka 0 Min 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2R, Helio Bordeaux BL, Bordeaux 1
0B, Bon Maroon Light, Bon Maroon Media, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thio Indigo Maroon, Permanent Red FGR, PV Carmine HR, Monolight Fast Red YS, Permanent Red BL, cobalt purple, manganese purple, fast violet B, methyl violet lake, dioxazine violet, ultramarine, navy blue, cobalt blue, cerulean blue, gosu, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue RS, Indanthrene Blue BC, Indigo, Chrome Green, Zinc Green, Chrome Oxide, Bi Zian, emerald green, cobalt green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, polybromide copper phthalocyanine, zinc sulfide, zinc silicate, zinc cadmium sulfide, calcium sulfide, strontium sulfide and Examples thereof include calcium tungstate.

In the present invention, one or more kinds (F) selected from a metal powder, a metal oxide powder or a glass powder having an ethylenically unsaturated bond present (introduced) on the surface are used. By using the powder (F), high sensitivity of the resin composition and the film can be achieved. In the present invention, one or more kinds selected from metal powder, metal oxide powder and glass powder having an ethylenically unsaturated bond on the surface (F)
Use By using the powder (F), high sensitivity of the resin composition and the film can be achieved. Specific examples of the metal powder, metal oxide powder, and / or glass powder which are components of the powder (F) include, for example, ruthenium oxide, yttrium oxide, europium oxide, samarium oxide, and oxide having a particle size of preferably 10 μm or less. Metal oxides or mixtures of cerium, lanthanum oxide, praseodymium oxide, neodymium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, etc., Y ₂ O ₃ : Eu, YVO ₄ : Eu,
(Y, Gd) BO ₃ : Eu, BaAl ₁₂ O ₁₉ : Mn, Z
_{n 2 SiO 4: Mn, BaMgAl} 14 O 23: Eu, Ba
MgAl ₁₆ O ₂₇ : Eu, MgO, LaB ₆ , Al, La
_0.5 Sr _0.5 CoO ₃ , La _0.7 Sr _0.3 : MnO
₃ etc., copper powder, silver powder, palladium powder, mixed powder of silver and palladium, surface-treated gold powder, lanthanum, cerium, samarium, praseodymium, neodymium, promethium, europium, gadolinium, terbium, dysprosium, holmium, thulium, erbium, ruthenium,
Examples thereof include metal powder or a mixture of yttrium and scandium, glass powder, glass beads, and the like. Due to these properties, the composition can be applied to a composition for a resistor, a composition for a conductor circuit, a composition for a phosphor, a composition for a partition, and the like.

The powder (F) used in the present invention can be obtained by introducing an ethylenically unsaturated bond into the powder surface exemplified above. The method of introducing these ethylenically unsaturated bonds is not particularly limited, but a method of treating the powder with a coupling agent having an ethylenically unsaturated bond, a method of coating the powder with a polymer having an ethylenically unsaturated bond, etc. preferable.

A method for treating a powder with a coupling agent having an ethylenically unsaturated bond will be described. The coupling agent having an ethylenically unsaturated bond is not particularly limited. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacrylic acid. Roxypropyltrimethoxysilane, vinylacetoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-
Glycidoxypropylmethyldiethoxysilane or γ-
Reaction product of a coupling agent having an epoxy group such as glycidoxypropylmethyldiethoxysilane and a (meth) acrylate having a carboxyl group such as (meth) acrylic acid, isocyanopropyltrimethoxysilane or isocyanopropyltriethoxy A reaction product of a coupling agent having an isocyanate group such as silane and a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is exemplified.

The method of treating the powder with the coupling agent is not particularly limited, but the dry method (the powder is mixed well with a V-type mixer or a Henschel mixer or the like, and after spraying the silane coupling agent aqueous solution, Drying), wet method (disperse powder in water or organic solvent to form slurry, add silane coupling agent while stirring, dehydrate and dry) or spray method (silane powder added to hot powder) Spraying an aqueous solution of a phosphorus agent). The processing amount of the silane coupling agent to the powder is preferably 0.5 to 2% by weight.

The polymer used in the method of coating a powder with a polymer having an ethylenically unsaturated bond is not particularly limited, but an acrylic resin, a urethane resin, an epoxy resin, a polyester resin, a polyether resin having an ethylenically unsaturated bond is used. , Polyamide resins, polyimide resins, polysulfide resins, melamine resins, cellulose resins, chitin, chitosan, gelatin and the like.

As a coating method of these polymers, a pan coating method, a hybridization method,
Mechanical fusion method, heat fusion method, solvent fusion method, spray drying method, coacervation method, interfacial polymerization method and in
The -situ method is exemplified. The thickness of these polymer layers is preferably 0.001 to 0.1 μm.

The resin composition of the present invention is obtained by dissolving, mixing, and dissolving each of the components (A) and / or (A '), (B), (C), (D) and / or (E) and (F). It can be prepared by kneading. In the resin composition of the present invention, the use ratio of each component can be as follows (% is% by weight). The total amount of (A) + (B-1) + (C) used is preferably from 5 to 60%, particularly preferably from 10 to 50%, based on the composition. (F) The component is 40-
It is preferably 95%, particularly preferably 50 to 90%. The added amount of the component (D) or (E) is (A) + (B−
Based on 1), it is preferably 0.0001 to 20%, particularly preferably 0.005 to 10%. (A) + (B−
(1) The preferred amount of each component occupying in the total amount of (C) is as follows: (A) 30-90%, (B-
The amount of component 1) used is 5 to 65%, and the amount of 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.

The resin composition of the present invention comprises, as described above, 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. After application,
If necessary, pre-baking is carried out 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. UV exposure is 10
It is preferably from 1 to 10,000 mJ / cm ² . Next, the liquid temperature is 10-60 ° C.
Is developed by a method such as spraying with an organic solvent, and then baked at, for example, 400 to 1000 ° C. for 1 to 24 hours to form a pattern.

As the organic solvent used as the developing solution,
Propane, n-butane, n-pentane, n-hexane,
Isohexane, n-heptane, n-octane, isooctane, n-decane, 2,2-dimethylbutane, petroleum ether, petroleum benzene, ligroin, gasoline, kerosene, petroleum spirit, petroleum naphtha, ethylene, 2-pentene, mixed pentene, Cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamylbenzene, triamylbenzene, tetraamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, coal tar naphtha , Solvent naphtha and other hydrocarbons, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, ethylene chloride, ethylidene chloride, 1,1,1-trichloroethane, 1,1,2-trice Roetan, 1,1,1,2
Halogenated hydrocarbons such as tetratururoethane and 1,1,2,2-tetrachloroethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n -Amyl alcohol, 3-pentanol, fuser oil, n-hexanol, methyl amyl alcohol, 2
-Ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 2-ethylhexanol, 3,3,5-trimethylhexanol, nonanol, n-decanol, undecanol, n Alcohols such as dodecanol, cyclohexanol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, α-terpineol, ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, methyl phenyl ether, ethyl phenyl ether, n −
Ethers and acetals such as butyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, diethyl ketone, cyclohexanone, methyl cyclohexanone Esters such as methyl formate, methyl formate, isobutyl formate, ethyl acetate, n-butyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl butyrate, ethyl lactate, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol Monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, polyhydric alcohols such as propylene glycol monomethyl ether acetate, monomethylamine, dimethylamine,
Trimethylamine, monoethylamine, diethylamine, triethylamine, isopropylamine, n-butylamine, ethylenediamine, aniline, cyclohexylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylformamide, acetonitrile, benzonitrile, pyridine, morpholine, ethyl Examples thereof include nitrogen compounds such as morpholine and phenylmorpholine, carbon disulfide, and dimethyl sulfoxide. These organic solvents may be used alone, or two or more kinds may be mixed, and water may be added as necessary.

A surfactant may be added to the developer. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and polyoxyethylene sorbitan alkyl esters.

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.

[0036]

The present invention will be described below with reference to Examples 1 to 5 and Comparative Examples. In the examples, “parts” means “parts by weight”. According to the composition shown in Table 1, a partition and a resin composition for a phosphor were prepared. The obtained resin composition is applied on the entire surface of the glass substrate with a thickness of 130 μm (dry film thickness) using a guide,
After pre-baking for 30 minutes in a negative film (line /
(Space = 150 μm / 150 μm) and irradiated with 500 mJ / cm ² by an ultra-high pressure mercury lamp, and then the unexposed area 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 (Synthesis Example of Reactant (A)) A round-bottomed flask equipped with a stirrer and a condenser was charged with a copolymerizable epoxy resin (Nippon Yushi Co., Ltd., Blenmer CP-50M, epoxy equivalent 31).
0, average molecular weight 6000) 310 parts, acrylic acid 72
, 1.8 parts of triphenylphosphine, 0.3 parts of methylhydroquinone and 500 parts of propylene glycol monomethyl ether acetate, heated to 60 ° C and dissolved, reacted at 95 ° C for 32 hours, and then reacted with succinic anhydride 98.
And reacted at 90 ° C. for 5 hours to obtain an average molecular weight of about 8
000, a polycarboxylic acid resin having an unsaturated group having a resin solid content of about 50%.

Preparation Example 1 (Preparation Example of Powder (F)) One part of γ-methacryloxypropyltrimethoxysilane and 0.05 part of acetic acid were dissolved in 100 parts of water to obtain an aqueous solution of a silane coupling agent. Average particle size 5
100 parts of low-melting glass powder of 100 μm is heated to 100 ° C., sprayed with an aqueous solution of a silane coupling agent while stirring well, and further dried for 5 hours at 100 ° C. to obtain a low-melting glass having an ethylenically unsaturated bond on its surface. Powder was obtained.

Preparation Example 2 (Preparation Example of Powder (F)) In 100 parts of water, 5 parts of the sodium salt of the resin synthesized in the synthesis example were dissolved, and 100 parts of a low-melting glass powder having an average particle size of 5 μm were uniformly dispersed. I let it. This dispersion was dried with a spray drier to obtain a low-melting glass powder having an ethylenically unsaturated bond on the surface.

[0040]

Table 1 Example 1 Comparative Example 1 2 3 4 Polymer solution obtained in synthesis example 20.0 12.0 12.0 Paogen EP-15 * 1 10.0 6.0 Tetraethylene glycol diglycidyl 5.0 3.0 Diacrylate of ether KAYARAD THE-330 * 2 5.0 2.5 2.5 KAYARAD TPGDA * 3 3.0 2.0 KAYACURE DETX-S * 4 0.25 0.1 0.5 0.5 0.25 KAYACURE EPA * 5 0.25 0.1 0.5 0.5 0.25 Irg-651 * 6 0.1 0.1 Glass powder obtained in Preparation Example 1 30 30 Preparation Example 2 30 30 Glass powder obtained in step 30 30 Glass powder 30 RUVA93 * 7 0.01 0.01 Residual organic matter (wt%) 0.2 0.3 0.1 0.15 0.15 Developability (1% sodium carbonate aqueous solution) ○ ○-Developability (water) ○ ○ Pattern after development State ○ ○ ○ ○ × Adhesion ○ ○ ○ ○

Note * 1 Paogen EP-15: polyether polyester polymer (Daiichi Kogyo Seiyaku Co., Ltd.) * 2 KAYARAD THE-330: EO-modified trimethylolpropane triacrylate (Nippon Kayaku Co., Ltd.)
* 3 KAYARAD NPGDA: neopentyl glycol diacrylate (Nippon Kayaku Co., Ltd.) * 4 KAYACURE DETX-S: 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) * 5 KAYACURE EPA: Nippon Kayaku Manufactured by Yakuhin Co., Ltd.
p-Dimethylaminobenzoic acid ethyl ester * 6 Irg-651: manufactured by Ciba-Geigy Corporation, 2,
2-Dimethoxy-1,2-diphenylethan-1-one * 7 RUVA93: 2- (2-'hydroxy-5'-
(Methacryloxyethylphenyl) -2H-benzothiazole (manufactured by Otsuka Chemical Co., Ltd.)

Example 5 The resin composition of Example 1 was applied to a release film so that the film thickness after drying became 130 μm, and dried at 80 ° C. for 30 minutes to obtain a film. Transfer this film to a glass substrate,
500mJ / c with extra high pressure mercury lamp after contacting negative film
m ² is irradiated, then developed for 2 minutes unexposed portion at a spray pressure 2 kg / cm ² in MEK (40 ℃). After the development, baking was performed at 500 ° C. for 1 hour in the air to form a partition wall 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 all ○.

(Residual organic content): The weight loss after heating and baking at 450 or 600 ° C. for 30 minutes was measured. (Developability): An organic solvent-based developer was used at a liquid temperature of 40 ° C. and a spray pressure of 2 kg / cm ² . Minutes, and evaluated as follows: ○: Completely developed △: Slight residue ×: Some parts were not developed-: Part of the pattern or The whole is peeled off (the state of the pattern after development): ・: The pattern is accurately maintained △: The width of the pattern is narrow ×: Part of the pattern portion Or, all are peeled off (adhesion): Cellophane tape peeling test was performed ○ ・ ・ ・ ・ No peeling at all △ ・ ・ ・ ・ Partial peeling × ・ ・ ・ ・ Many peeling parts

As is clear from the results of Examples 1 to 5 and Comparative Example, the resin composition, film and cured product of the present invention have excellent developability, good pattern accuracy after development, and
Low residual organic matter after firing and excellent adhesion.

[0045]

The resin composition and film of the present invention are selectively exposed to ultraviolet light through a film on which a pattern is formed, and are developed by developing an unexposed portion to form a pattern of a resistor, a phosphor, a partition or a conductor circuit. In formation
It has excellent developability, good pattern accuracy after development, little residual organic matter even when fired at low temperatures, and excellent adhesion.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08L 101/00 LTB C08L 101/00 LTB G03F 7/027 502 G03F 7/027 502 H01J 9/02 H01J 9/02 F 9/227 9/227 C

Claims (6)

[Claims] 1. A photopolymerizable resin compound (A) and / or a non-reactive resin (A '), a diluent (B), a photopolymerization initiator (C) and an ethylenically unsaturated bond present on the surface. A resin composition containing one or more (F) selected from among metal powders, metal oxide powders and glass powders, and developable with water, an aqueous alkali solution or an organic solvent. 2. Photopolymerizable resin compound (A) and / or non-reactive resin (A '), diluent (B), photopolymerization initiator (C), ultraviolet absorber (D) and / or coloring Agent (E),
And one or more (F) selected from metal powder, metal oxide powder or glass powder having an ethylenically unsaturated bond on the surface, and can be developed with water, an aqueous alkali solution or an organic solvent. Resin composition. 3. The resin composition according to claim 1, which is used for a resistor pattern, a conductor pattern, a phosphor pattern or a partition pattern. 4. A film comprising the resin composition according to claim 1, 2 or 3. 5. A cured product of the resin composition according to claim 1, 2, 3, or 4. 6. A resistor, a conductor, a phosphor and a partition wall obtained by firing the cured product according to claim 5.