JPH09208640A - Resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can give elaborate patterns and gives good resistor patterns, phosphor patterns, diaphragm patterns or conductor circuit patterns by mixing a specified reaction product with a diluent, a photopolymerization initiator, and a metal powder, a metal oxide or a glass powder. SOLUTION: This composition comprises a reaction product prepared by reacting a polymer (d) obtained by polymerizing an ethylenically unsaturated monomer represented by the formula (wherein R1 is H or methyl; R2 is hydrogen or an alkyl; and (n) is 2-40) and/or a glycerol (meth)acrylate (a) with a compound (b) having one (meth)acryloyl group and one vinyl or epoxy group in the molecule and optionally ethylenically unsaturated monomer (c) copolymerizable with compound (a) and (b) with a compound (e) having one (meth)acryloyl or vinyl group and one carboxyl group in the molecule and reacting the obtained product with a compound (f) obtained by replacing the carboxyl group of compound (e) with an isocyanate group, a diluent, a photopolymerization initiator, and at least one member selected from among metal powders, metal oxides and glass powders.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is preferably used in a manufacturing process of a resistor pattern, a conductor circuit pattern or a fluorescent substance pattern, a partition wall or the like used in a plasma display, a fluorescent display tube, an electronic component, etc. 400 to 1 after development with weak alkaline aqueous solution or water
A resin composition for forming a good resistor pattern, a circuit pattern having excellent conductivity, a fluorescent substance pattern, partition walls, or the like for stably flowing an electric current by firing at 000 ° C., a cured product thereof, and firing. Regarding molded products.

[0002]

2. Description of the Related Art Conventionally, resistors, phosphors and barriers for plasma displays, fluorescent display tubes, etc., or conductors for circuits have been formed by resistor pastes (resist pastes), fluorescent pastes ( Fluorescent material in paste form), partition paste (partition material in paste form) and conductor paste (conductive material in paste form such as copper powder, silver powder) are pattern printed by screen printing etc. It is known to form a resistor pattern, a phosphor pattern and a partition pattern, or a conductor circuit pattern by firing next. However, these are resistor patterns, fluorescent patterns, barrier rib patterns, and
Alternatively, it cannot be applied to the high density and fine line pattern of the conductor circuit pattern. Also, the thermal decomposition temperature of the resin component is high,
It was difficult to sufficiently fulfill the functions of the resistor, the conductor, the phosphor, and the partition because of the residue of the organic substance after firing.

[0003]

DISCLOSURE OF THE INVENTION The present invention improves the above-mentioned drawbacks and enables fine pattern formation. After curing with ultraviolet rays, development with a weak alkaline aqueous solution (eg, 1% sodium carbonate aqueous solution) or water is carried out. Provided is a resin composition which forms a good resistor pattern, phosphor pattern, partition wall pattern or conductor circuit pattern due to the low thermal decomposition temperature of the resin component, and a cured product thereof.

[0004]

The present invention provides [1] a general formula (1)

[0005]

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(Wherein R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or an alkyl group, and n is an integer of 2 to 30) and / or Glycerol mono (meth) acrylate (a), compound (b) having one (meth) acryloyl group or one vinyl group and one epoxy group in one molecule, (a) as an optional component
And a polymer (d) obtained by polymerizing a copolymerizable ethylenically unsaturated monomer (c) other than the component (b) has one (meth) acryloyl group or vinyl group and one carboxyl group in one molecule. After reacting the compound (e) having each of them,
Reaction product (A) with a compound (f) having one (meth) acryloyl group or vinyl group and one isocyanate group in one molecule, diluent (B), photopolymerization initiator (C), metal powder, metal A resin composition containing one or more kinds (D) selected from oxides or glass, [2] resistor pattern, conductor pattern, phosphor pattern or partition pattern. [1] The resin composition described in [1], [3] a cured product of the composition described in [1] and [2], [4] a resistor and a conductor obtained by firing the cured product described in [3]. , Phosphors and barrier ribs.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the present invention, the polymer (d) is reacted with a compound (e) having one (meth) acryloyl group or one vinyl group and one carboxyl group in one molecule, and then (meth) acryloyl group is contained in one molecule. Alternatively, a reaction product (A) of a compound (f) having one vinyl group and one isocyanate group is used. The polymer (d) used in the present invention can be obtained by a known polymerization method such as solution polymerization or emulsion polymerization. Explaining the case of solution polymerization, a mixture of an ethylenically unsaturated monomer comprising the above components (a), (b) and (c) is added with a polymerization initiator in an applicable organic solvent, and the mixture is placed under a nitrogen stream. Polymerization is preferably carried out by heating and stirring at 50 to 100 ° C. Examples of the organic solvent include ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol,
Alcohols such as 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, and dipropylene glycol methyl ether. Polypropylene glycol alkyl ethers, ethyl acetate, butyl acetate, cellosolve acetate,
Examples thereof include acetic acid esters such as propylene glycol monomethyl acetate, lactate esters such as ethyl lactate and butyl lactate, and dialkyl glycol ethers.
These organic solvents can be used alone or as a mixture.

As the polymerization initiator, for example, a peroxide such as benzoyl peroxide or an azo compound such as azobisisobutyronitrile can be used.

As the component (a), an ethylenically unsaturated monomer represented by the general formula (1), for example, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) is used. ) Polyethylene glycol mono (meth) acrylates such as acrylates, methoxydiethylene glycol mono (meth) acrylates, methoxytriethylene glycol mono (meth) acrylates, methoxytetraethylene glycol mono (meth) acrylates, and other alkoxy polyethylene glycol (meth) acrylates Is mentioned. These ethylenically unsaturated monomers and glycerol mono (meth) acrylate can be used alone or in combination.

The component (a) is used in the polymer (d) for the purpose of improving the water solubility of the reaction product (A) of the present invention, and the unsaturated components (a), (b) and (c) are used. It is desirable to add 20% by weight or more, particularly preferably 30% by weight or more to the total amount of the monomers. Further, the polymerization average molecular weight of the polymer (d) is preferably about 10,000 to 200,000. The molecular weight of the reaction product (A) is preferably 20,000 to 500,000.

Examples of the component (b) include glycidyl methacrylate and glycidyl acrylate.
The component (b) is used in the polymer (d) (a), (b).
10 to 70% by weight, and particularly preferably 10 to 50% by weight, based on the total amount of unsaturated monomers (c).

Specific examples of the component (c) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acryl. Acid, (meth) acrylamide, N
-Methyl (meth) acrylamide, styrene, etc. can be mentioned. The component (c) is 0 based on the total amount of unsaturated monomers (a), (b) and (c) used in the polymer (d).
~ 70% by weight is preferred.

Component (e), for example, (meth), per 1 equivalent of epoxy group of the polymer (d) thus obtained
It is preferred to react 0.5 to 1.1 equivalents of acrylic acid. In order to accelerate the reaction, 0.1 to 1% of a basic compound such as triphenylphosphine, triphenylstibine, triethylamine, triethanolamine, tetramethylammonium chloride, benzyltriethylammonium chloride as a reaction catalyst is added to the reaction solution. Preferably. 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 70 hours.

Examples of the compound (f) having one (meth) acryloyl group or vinyl group and one isocyanate group in one molecule include methacryloyloxyethyl isocyanate and m-isopropenyl-α, α-dimethylbenzyl isocyanate. It is illustrated. These compounds are usually used in an amount of 0.1 equivalent to 1 equivalent of the epoxy group of the polymer (d).
It is preferable that the reaction is carried out in an amount of up to 1.1 equivalents, more preferably 0.5 to 0.9 equivalents. The reaction temperature is 70 to 150.
C. and reaction time are preferably 1 to 20 hours. Further, if necessary, 0.01 to 5% of dibutyltin dilaurate may be added as a reaction catalyst.

The diluent (B) is used in the present invention.
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, benzyl dimethyl ketal and 2-ethyl anthraquinone. 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 metal powder, metal oxide or glass (D) include, for example, ruthenium oxide, yttrium oxide, europium oxide, samarium oxide, cerium oxide, lanthanum oxide, and oxide having a particle size of preferably 10 μm or less. Metal oxides or mixtures of praseodymium, neodymium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, etc., copper powder, silver powder, palladium powder, mixed powder of silver and palladium, surface-treated Metal powder or mixture of gold powder, lanthanum, cerium, samarium, praseodymium, neodymium, promethium, europium, gadolinium, terbium, dysprosium, holmium, thulium, erbium, ruthenium, yttrium, scandium, etc., glass powder Glass beads, particularly _{preferably, Y 2 O 3: Eu,} YVO 4: Eu, (Y, Gd) B
_{O 3: Eu, BaAl 12 O} 19: Mn, Zn 2 SiO 4:
Mn, BaMgAl ₁₄ O ₂₃ : Eu, BaMgAl
₁₆ O ₂₇ : Eu, MgO, LaB ₆ , Al, La _0.5 Sr
_{0.5 CoO 3, La 0.7 Sr 0.3} : can be exemplified MnO ₃ and the like. Due to the characteristics possessed by them, they can be applied to a resistor composition, a conductor circuit composition, a phosphor composition, a partition composition, and the like.

The resin composition of the present invention comprises (A), (B),
It can be prepared by dissolving, mixing and kneading the components (C) and (D). In the resin composition of the present invention,
The usage ratio of each component can be set 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. The component (D) is contained in the composition,
40 to 95% is preferable, and 50 to 90% is particularly preferable.
It is. The preferable amount of each component used in the total amount of (A) + (B-1) + (C) is as follows. That is, the amount of the component (A) used is 30 to 90%, (B-1)
The amount of the component used is 5 to 65%, and 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.

The resin composition of the present invention contains a leveling agent, a defoaming agent, a coupling agent, a polymerization inhibitor, waxes and non-reactive polymers (eg, polyethylene glycol, polyethylene glycol, etc.) as long as its performance is not impaired. It is also possible to use polyester, acrylic polymer, cellulose, etc., which is a reaction product of a polybasic acid or its anhydrous acid), and the like.

As described above, the resin composition of the present invention is a resistor composition, a phosphor resin composition, a partition resin composition,
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
0 to 10000 mJ / cm ² is preferable. Liquid temperature 10-60
Development is carried out by a means such as spraying using a developing solution such as a dilute alkaline aqueous solution (eg, 1% sodium carbonate aqueous solution, 1% caustic soda aqueous solution) or water at 0 ° C., and then, for example, 1 to 24 at 400 to 1000 ° C. Bake for a time to form a pattern.

[0021]

EXAMPLES The present invention will be described below with reference to Examples 1-8. In the examples, “parts” means “parts by weight”. A resin composition for a resistor or a phosphor was prepared according to the composition shown in Table 1. The resin composition thus obtained was coated on a glass substrate with a 150-mesh polyester screen to form a film having a thickness of 35 μm.
After applying (dry film thickness) and pre-baking at 80 ° C. for 30 minutes, a negative film is brought into contact with the film and applied with an ultra-high pressure mercury lamp for 15 minutes.
Irradiate with 00 mJ / cm ² and then spray the unexposed area with a 1% sodium hydrogen carbonate aqueous solution or water (40 ° C.) to a spray pressure of 2
It was developed at kg / cm ² for 2 minutes. After development, in air, 450-
The pattern was fired at 600 ° C. for 1 hour to form a resistor 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 of Reactant (A)) Synthesis Example 1 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 under a nitrogen stream at 75 ° C. Polymerization was carried out for 5 hours to obtain a 50% polymer (d-1) solution. This 50% polymer (d
-1) 300 parts of a solution, 22.8 parts of acrylic acid, 0.16 parts of methylhydroquinone, and 0.3% of triphenylphosphine.
After mixing and dissolving 9 parts and reacting at 95 ° C. for 32 hours,
45 parts of methacryloyloxyethyl isocyanate and 0.05 part of dibutyltin dilaurate were added and reacted at 80 ° C. for 12 hours to obtain a reaction product (A-1) solution (solid content 58%). The polymerization average molecular weight of the reaction product (A-1) was about 120,000 [measured by GPC (gel permeation chromatography); the same applies hereinafter)].

Synthesis Example 2 50 parts of tetraethylene glycol monomethacrylate,
Glycidyl methacrylate (25 parts), methyl methacrylate (25 parts), propylene glycol monomethyl ether acetate (100 parts) and azobisisobutyronitrile (2 parts) were added and the mixture was heated under a nitrogen stream and polymerized at 75 ° C for 5 hours to give a 50% polymer (d -2) A solution was obtained. Then
300 parts of this 50% polymer (d-1) solution, 19 parts of acrylic acid, 0.16 parts of methylhydroquinone, and 0.9 parts of triphenylphosphine were mixed and dissolved, and the mixture was reacted at 95 ° C. for 32 hours, and then meta-chrome. 40 parts of yloxyethyl isocyanate and 0.05 part of dibutyltin dilaurate were added and reacted at 80 ° C. for 12 hours to obtain a solution (A-2) (solid content 57%). The polymerization average molecular weight of the reaction product (A-2) was about 80,000.

Synthesis Example 3 Methoxynonaethylene glycol monomethacrylate 5
0 parts, 20 parts of glycidyl methacrylate, 30 parts of methyl methacrylate, 100 parts of phenoxyethanol, 3 parts of benzoyl peroxide were added, heated under a nitrogen stream and polymerized at 75 ° C. for 5 hours to give a 50% polymer (d-
3) A solution was obtained. Then, this 50% polymer (d-3)
After 300 parts of the solution, 15.0 parts of acrylic acid, 0.16 parts of methylhydroquinone and 0.9 parts of triphenylphosphine were mixed and dissolved and reacted at 95 ° C. for 32 hours, 32 parts of methacryloxyethyl isocyanate, dilaurin 0.05 part of dibutyltin acid salt was added and reacted at 80 ° C. for 12 hours to obtain a reaction product (A-3) solution (solid content 57%).
The polymerization average molecular weight of the reaction product (A-3) was about 170,000.

[0025]

[Table 1] Table 1 Example 1 2 3 4 Polymer solution (A-1) 24.6 12.3 obtained in Synthesis Example 1 Polymer solution (A-2) 24.6 obtained in Synthesis Example 2 Obtained in Synthesis Example 3 Polymer solution (A-3) 11.0 Tetraethylene glycol diglycidyl 3.0 1.0 13.0 Diacrylate of ether KAYARAD PEG400DA * 1 3.0 2.0 KAYARAD DPHA * 2 3.0 2.0 KAYACURE DETX-S * 3 0.5 0.5 0.5 0.5 KAYACURE EPA * 4 0.5 0.5 0.5 0.5 Mixture of ruthenium oxide and glass powder 30 30 30 30 Residual organic matter (wt%) 0.2 0.3 0.1 0.15 Developability (water) ○ ○ ○ ○ Pattern condition after development ○ ○ ○ ○ Adhesion ○ ○ ○ ○

[0026]

[Table 2] Table 2 Example 5 6 7 8 Polymer solution (A-1) 11.0 obtained in Synthesis Example 1 Polymer solution (A-2) 11.0 obtained in Synthesis Example 2 Weight obtained in Synthesis Example 3 Combined solution (A-3) 11.0 6.0 Irg-651 * 5 0.3 0.3 0.3 0.15 Phosphor powder * 6 30 30 30 30 Residual organic matter (wt%) 0.2 0.3 0.1 0.15 Developability (water) ○ ○ ○ ○ Pattern after development State of ○ ○ ○ ○ Adhesion ○ ○ ○ ○

Note * 1 KAYARAD PEG400DA: manufactured by Nippon Kayaku Co., Ltd., polyethylene glycol diacrylate * 2 KAYARAD DPHA: Nippon Kayaku Co., Ltd.
Mixture of dipentaerythritol penta and hexaacrylate * 3 KAYACURE DETX-S: Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone, photopolymerization initiator * 4 KAYACURE EPA: Nippon Kayaku Co., Ltd.
P-dimethylaminobenzoic acid ethyl ester * 5 Irg-651: manufactured by Ciba-Geigy Co., Ltd.
2,2-Dimethoxy-1,2-diphenylethane-1-
ON * 6 Y ₂ O ₃ : Eu

(Residual organic content): Measure the weight loss after heating and baking at 450 or 600 ° C. for 30 minutes (Developability): 1% sodium hydrogen carbonate aqueous solution or water,
Development was performed at a liquid temperature of 40 ° C. and a spray pressure of 2 kg / cm ² for 2 minutes, and the evaluation was made as follows: ・ ・ ・ ・ Complete development was possible △ ・ ・ ・ ・ Slight residue was left × ・ ・ ・ ・ No development There is a portion (the state of the pattern after development): ○ ・ ・ ・ ・ The pattern is maintained accurately △ ・ ・ ・ ・ The width of the pattern is narrower × ・ ・ ・ ・ Part of the pattern portion or All are peeled off (adhesion): Cellotape peeling test was conducted ○ ・ ・ ・ ・ No peeling at all △ ・ ・ ・ ・ There is very little peeling × ・ ・ ・ ・ Many peeled portions

As is clear from the results of Tables 1 and 2, the resin composition of the present invention and the cured product thereof have excellent developability, good pattern accuracy after development, and little organic matter remaining after firing. Excellent adhesion.

[0030]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is used for patterning a resistor, a fluorescent substance, a partition wall or a conductor circuit by selectively exposing it to ultraviolet rays through a film having a pattern and developing the unexposed portion. Excellent in developability, good pattern accuracy after development, little organic matter remains even when baked at low temperature, and excellent in adhesion.

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Claims (4)

[Claims] 1. A compound of the general formula (1) (In the formula, R ₁ is hydrogen or a methyl group, R ₂ is a hydrogen or an alkyl group, and n is an integer of 2 to 30.) and an ethylenically unsaturated monomer and / or glycerol mono ( (Meth) acrylate (a), compound (b) having one (meth) acryloyl group or one vinyl group and one epoxy group in one molecule, and copolymerizable ethylene other than the components (a) and (b) as an optional component After reacting a compound (e) having one (meth) acryloyl group or one vinyl group and one carboxyl group in one molecule with a polymer (d) obtained by polymerizing a water-soluble unsaturated monomer (c) Reaction product (A) obtained by reacting compound (f) having one (meth) acryloyl group or vinyl group and one isocyanate group in one molecule, diluent (B), photopolymerization initiator (C), metal powder,
A resin composition containing one or more kinds (D) selected from metal oxides and glasses. 2. The resin composition according to claim 1, which is for a resistor pattern, a conductor pattern, a phosphor pattern or a partition pattern. 3. A cured product of the composition according to claim 1 or 2. 4. A resistor, a conductor, a phosphor and a partition obtained by firing the cured product according to claim 3.