JPH09316112A - Resin composition, and film and cured substance prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition, a film prepd. therefrom and a cured substance prepd. therefrom which are usable for preparing a patterned resistance and the like, and which enable not only the development with water or an aqueous alkaline solution, but also the preparation of a product which is excellent with respect to accuracy of formed patterns and has a very small conent of organic residues remaining after heating and calcination and further exhibits excellent adhesiveness. SOLUTION: Polymer A is prepd. by reacting a polymer (c), which is a polymer prepd. from a compound (a) having one (meth)acryloyl or vinyl group and one glycidyl group in one molecule thereof and an ethylenically unsaturated monomer (b) being copolymerizable with (a), with a compound (d) obtained by aminating one of the terminals of an oligo or polyethylene glycol and a compound (e) having one (meth) acryloyl or vinyl group and one carboxyl group in one molecule thereof. This resin composition comprises polymer A or a compound A' which is prepd. by adding a polycarboxylic acid anhydride to polymer A, a diluent B, a photopolymerization initiator C, at least one member D selected from the group consisting of a metal powder, a metal oxide and glass.

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 phosphor pattern, a partition wall or the like used in a plasma display, a fluorescent display tube, an electronic part, 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 film thereof, and a cured product thereof. And a fired molded product.

[0002]

2. Description of the Related Art Conventionally, resistors, phosphors and barrier ribs for plasma displays, or circuit conductors have been used as resistor pastes (resist pastes), fluorescent pastes (fluorescent pastes). Shape), partition paste (paste material for the partition) and conductor paste (paste conductive material such as copper powder, silver powder, etc.) by pattern printing by screen printing, and then firing. It is known that a resistor pattern, a fluorescent substance pattern, a partition pattern, or a conductor circuit pattern is formed by the above method. However, these cannot cope with the recent high density, fine line pattern of the resistor pattern, the fluorescent pattern, the partition pattern, or the conductor circuit pattern.
Further, in the step of applying the paste to the substrate, it is difficult to apply a uniform film thickness when the size of the substrate is large, so the obtained resistors, phosphors, partition walls and conductors tend to vary in specification. . Further, the conventional resin component has a relatively high thermal decomposition temperature, and it is difficult to sufficiently fulfill the functions of the resistor, the conductor, the phosphor and the partition wall due to the residue of the organic matter 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 are a resin composition which forms a good resistor pattern, a fluorescent substance pattern, a partition wall pattern or a conductor circuit pattern, and a cured product thereof, in which a residue of an organic substance is small due to a low thermal decomposition temperature of a resin component in a firing step. . Further, instead of the conventional printing method, a uniform film thickness can be secured by forming a film of this composition and applying it to a substrate.

[0004]

MEANS FOR SOLVING THE PROBLEMS The present invention is [1] copolymerizable with compounds (a) and (a) each having one (meth) acryloyl group or vinyl group and one glycidyl group in one molecule. The polymer (c) of the ethylenically unsaturated monomer (b) has one amino terminal compound (d) of oligo or polyethylene glycol and one (meth) acryloyl group or vinyl group and one carboxyl group in one molecule. Polymer (A) obtained by reacting compound (e), diluent (B), photopolymerization initiator (C), one or more selected from metal powder, metal oxide or glass. A resin composition containing (D), [2] a compound (A ′) obtained by adding an acid anhydride of a polycarboxylic acid to the polymer (A) described in [2] above, diluted Agent (B), photopolymerization initiator (C),
A resin composition containing one or more kinds (D) selected from metal powder, metal oxides or glass, [3] resistor pattern, conductor pattern, phosphor pattern or The resin composition according to the above [1] and [2] for a partition pattern, [4] a film comprising the composition according to the above [1], [2] and [3], [4] above [1],
A cured product of the composition according to [2], [3] and [4],
[6] A resistor, a conductor, a phosphor and a partition obtained by firing the cured product according to [5] above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polymer (c) 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) and (b)
The ethylenically unsaturated monomer mixture composed of the components is polymerized by adding a polymerization initiator in an applicable organic solvent and heating and stirring under a nitrogen stream, preferably at 50 to 100 ° C. Examples of the organic solvent include 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, carbitol, carbitols such as butyl carbitol, propylene glycol alkyl ethers such as propylene glycol methyl ether, polypyropyrene glycol alkyl ethers such as dipropylene glycol methyl ether, ethyl acetate, Acetic acid esters such as butyl acetate, cellosolve acetate, propylene glycol monomethyl acetate, butyl carbitol cetate, ethyl lactate, milk Lactic acid esters such as butyl,
Dialky glycol ethers etc. are mentioned. These organic solvents can be used alone or in combination.

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

Examples of the component (a) include glycidyl methacrylate and glycidyl acrylate. The component (a) is preferably 10 to 100% by weight, and particularly preferably 20 to 80% by weight, based on the total amount of unsaturated monomers (a) and (b) used in the polymer (c).

Specific examples of the component (b) 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 (b) is 0 to 90 based on the total amount of the unsaturated monomers (a) and (b) used in the polymer (c).
Weight% is preferred, and particularly preferred is 20-80%. The molecular weight of the polymer (c) is about 10,000 to 20.
0000 is preferred.

As the compound (d) used in the present invention, for example, a compound (PEG) obtained by adding acrylonitrile to methoxyethylene glycol, methoxydiethylene glycol, methoxypolyethylene glycol or the like and then hydrogenating the same.
-NH2) and the like are exemplified.

Examples of the compound (e) include acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, and acid anhydrides of polycarboxylic acid compounds. (For example, succinic acid-free, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) and hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, glycerin diacrylate,
Examples thereof include a half ester which is a reaction product with trimethylolpropane diacrylate and pentaerythritol triacrylate.

The polymer (c) can be reacted with (d) and (e) to obtain the polymer (A) of the present invention. (C)
It is preferable to react 0.1 to 0.9 equivalent of (d) and 0.1 to 0.9 equivalent of (e) with 1 equivalent of the epoxy group. 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, methyl haloidroquinone, hydroquinone, phenothiazine, etc.) in an amount of 0.05 to 0.5% in the reaction solution in order to prevent polymerization. The reaction temperature is preferably 90 to 150 ° C., and the reaction time is preferably 5 to 70 hours.

The compound (A ') used in the present invention is (A)
It is obtained by adding an acid anhydride of polycarboxylic acid to. Examples of acid anhydrides of polycarboxylic acids include succinic acid-free, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride, but are not particularly limited thereto. The reaction temperature is preferably 60 to 100 ° C., and the reaction time is preferably 1 to 20 hours. The molecular weight of the polymer (c) is preferably 10,000 to 500,000.

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. Formolin, a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate) and an acid of a polycarboxylic acid compound Half ester, which is a reaction product of anhydrides (for example, succinic acid-free, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.), 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 and methyl isobutyl ketone, esters such as acetic acid ester and butyl acetate,
Aromatic hydrocarbons such as toluene, xylene, 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, which preferably have a particle size of 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, cadolinium, terbium, dysprosium, holmium, thulium, erbium, ruthenium, yttrium, scandium, etc., glass powder Mention may be made of 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 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, an antifoaming agent, a coupling agent, a polymerization inhibitor, waxes and non-reactive polymers (for example, 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
It is preferably from 1 to 10,000 mJ / cm ² . Next, the liquid temperature is 10-60 ° C.
Dilute alkaline aqueous solution (for example, 1% sodium carbonate aqueous solution,
1% caustic soda solution or the like) or a developer such as water is used for development by means such as spraying, and then, for example, 4
A pattern is formed by baking at 00 to 1000 ° C. for 1 to 24 hours.

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 method, a dipping method, a spin coating method, a gravure method, a doctor blade method, etc. If necessary, it is dried with far infrared rays or warm air at 50 to 250 ° C., and if necessary, a release film or the like is attached. When using, peel off the release film and transfer it to the substrate,
A pattern is formed by exposure, development and baking in the same manner as in the above [0019].

[0020]

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 resistors was prepared according to the composition shown in Table 1. The obtained resin composition was applied on the entire surface of a glass substrate with a film thickness of 35 μm (dry film thickness) using a 150-mesh polyester screen, prebaked at 80 ° C. for 30 minutes, and then contacted with a negative film to achieve ultrahigh pressure. Irradiation was performed with a mercury lamp at 1500 mJ / cm ² , and then the unexposed area was developed with a 1% aqueous sodium hydrogen carbonate solution or water (40 ° C.) at a spray pressure of 2 kg / cm ² for 2 minutes. After the development, the film was baked in air at 450 to 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 90 parts of glycidyl methacrylate, 10 parts of methyl methacrylate, 200 parts of butyl carbitol acetate and 2 parts of azobisisobutyronitrile were added and heated under a nitrogen stream, Polymerization was carried out at 75 ° C for 5 hours to obtain a 50% polymer (c-1) solution. Then, (c-1) solution 300
Part consisting of methoxytetraethylene glycol
99 parts of -NH2 was added and reacted at 60 ° C for 3 hours, and further 18 parts of acrylic acid and 0.16 of methylhydroquinone were added.
And 0.9 parts of triphenylphosphine are mixed and dissolved,
The reaction was carried out at 95 ° C. for 32 hours (A-1) solution (solid content 52
%) Was obtained. When the average molecular weight of the reaction product (A-1) was measured by GPC, it was about 80,000.

Synthesis Example 2 To 300 parts of the above (c-1) solution was added 152 parts of PEG-NH2 consisting of methoxynonaethylene glycol, and 60 parts were added.
Reacted for 3 hours at ℃, 22.5 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 to obtain a solution (A-2) (solid content 58%). Reaction product (A
The average molecular weight of -2) was about 120,000 as measured by GPC.

Synthesis Example 3 To 300 parts of the above (A-1) solution, 20 parts of maleic anhydride was added and reacted at 80 ° C. for 6 hours to obtain a (A′-1) solution (solid content 55%). The average molecular weight of the reaction product (A′-1) was measured by GPC, and it was about 80,000.

[0024]

[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 11.0 Tetraethylene glycol diglycidyl obtained in Synthesis Example 2 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 Ruthenium oxide and glass powder mixture powder 30 30 30 30 Remaining Organic matter (wt%) 0.2 0.3 0.1 0.15 Developability (water) ○ ○ ○ ○ Pattern condition after development ○ ○ ○ ○ Adhesion ○ ○ ○ ○

[0025]

[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 6.0 obtained in Synthesis Example 2 Obtained in Synthesis Example 3 Polymer solution (A'-1) 11.0 Irg-651 * 5 0.3 0.3 0.15 0.3 Fluorescent powder 30 30 30 30 Residual organic matter (wt%) 0.2 0.3 0.1 0.1 Developability (water) * 6 ○ ○ ○ ○ After development Pattern condition ○ ○ ○ ○ 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.
Manufactured by p-Dimethylaminobenzoic acid ethyl ester * 5 Irg-651: manufactured by Chiver Geigy Co., Ltd.
2,2-Dimethoxy-1,2-diphenylethane-1-
On * 6 Example 8 was developed with a 1% sodium carbonate aqueous solution.

Example 9 The resin composition of Example 7 was applied to a release film so that the film thickness after drying would be 50 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, then spray the unexposed area with water to a spray pressure of 2 kg
Development was carried out at / cm ² for 2 minutes. After development, 1 at 500 ° C in air
It was fired for a time 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 all ○.

(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 carried out at a liquid temperature of 40 ° C. and a spray pressure of 2 kg / cm ² for 2 minutes, and the evaluation was performed as follows. ○ ・ ・ ・ ・ Fully developed △ ・ ・ ・ ・ Slight residue is left × ・ ・ ・ ・ Some areas are not developed (state in pattern after development): ○ ・ ・ ・ ・ Pattern is maintained accurately △ ・ ・ ・ ・ The width of the pattern is narrower × ・ ・ ・ ・ ・ ・ Peeled off part or all of the pattern (adhesion): Cellotape peeling test was conducted ○ ・ ・ ・ ・ Peeled off at all No △ ・ ・ ・ ・ Peeled off very much × ・ ・ ・ ・ ・ ・ A lot of peeled off

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

[0030]

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
Excellent developability, good pattern accuracy after development, little residual organic matter even when baked at low temperature, and excellent adhesion.

Claims (6)

[Claims] 1. A compound (a) having one (meth) acryloyl group or one vinyl group and one glycidyl group in one molecule, and a copolymer of an ethylenically unsaturated monomer (b) copolymerizable with (a). Polymer obtained by reacting the compound (c) with an amino compound (d) having one terminal of oligo or polyethylene glycol and a compound (e) having one (meth) acryloyl group or vinyl group and one carboxyl group in one molecule. (A), diluent (B), photopolymerization initiator (C), one or more selected from metal powder, metal oxide or glass (D)
A resin composition comprising: 2. A compound (A ') obtained by adding an acid anhydride of a polycarboxylic acid to the polymer (A) according to claim 1, a diluent (B), a photopolymerization initiator (C), a metal. One or more selected from powder, metal oxide or glass (D)
A resin composition comprising: 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 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 obtained by firing the cured product according to claim 5.