JP2005122202A - Resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which can be developed with water, has good pattern accuracy, ensures little residue of organic matter after heat baking and forms a resistive pattern excellent in adhesion, etc., and to provide a cured product thereof. <P>SOLUTION: The resin composition comprises a polymer (A) of a specific structure obtained using a compound of formula (1) as starting material, a diluent (B), a photopolymerization initiator (C) and one or more (D) selected from metal powders, metal oxides or glass. The cured product thereof is also provided. In formula, R<SB>1</SB>is H or methyl; R<SB>2</SB>is H or alkyl; and n is an integer of 2-10. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is suitably used in the production process of resistor patterns, conductor circuit patterns or phosphor patterns or partition walls used for plasma displays, electronic parts, etc., and is 400 to 1000 after exposure with ultraviolet light, development with weak alkaline aqueous solution or water. The present invention relates to a resin composition that forms a good resistor pattern, a circuit pattern having excellent conductivity, a phosphor pattern, a partition wall, and the like, and a cured product thereof.

Conventionally, plasma display resistors, phosphors and barriers, or circuit conductors are resistor pastes (resistor pastes), phosphor pastes (phosphor pastes) Resistors by printing a pattern by screen printing etc., followed by firing a partition paste (a product obtained by pasting a partition material) and a conductive paste (a paste made of a conductive material such as copper powder or silver powder) A pattern, a phosphor pattern, a partition pattern, or a conductor circuit pattern is known. However, these cannot cope with the recent increase in density and thin line pattern of resistor patterns, phosphor patterns, barrier rib patterns, or conductor circuit patterns.
Japanese Patent Laid-Open No. 06-228442

  The present invention improves the above-mentioned drawbacks, enables fine pattern formation, is cured with ultraviolet light, and then developed with a weak alkaline aqueous solution (for example, 1% sodium carbonate aqueous solution) or water to form a resistor pattern and a phosphor pattern. A resin composition for forming a partition wall pattern or a conductor circuit pattern and a cured product thereof are provided.

［式中、Ｒ_１は水素又はメチル基、Ｒ_２は水素又はＣ１〜Ｃ５のアルキル基であり、ｎは２〜１０の整数である］で表されるエチレン性不飽和単量体及び／又はグリセロールモノ（メタ）アクリレート（ａ）３０重量％以上、（ａ）成分以外の（ａ）成分と共重合可能なエチレン性不飽和単量体（ｂ）７０重量％以下を重合させて得られる重合体（Ａ）、希釈剤（Ｂ）、光重合開始剤（Ｃ）、金属粉、金属酸化物又はガラスの中から選択される１種又は２種以上（Ｄ）を含有する事を特徴とする樹脂組成物、特に抵抗体パターン用樹脂組成物、導体回路パターン用樹脂組成物、螢光体パターン用樹脂組成物、隔壁パターン用樹脂組成物及びその硬化物に関する。 The present invention relates to a general formula (1)

[Wherein R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a C1-C5 alkyl group, and n is an integer of 2-10] and / or Weight obtained by polymerizing glycerol mono (meth) acrylate (a) 30% by weight or more and ethylenically unsaturated monomer (b) 70% by weight or less copolymerizable with component (a) other than component (a) 1 type or 2 types or more (D) selected from coalescence (A), a diluent (B), a photoinitiator (C), a metal powder, a metal oxide, or glass are characterized by the above-mentioned The present invention relates to a resin composition, in particular, a resistor pattern resin composition, a conductor circuit pattern resin composition, a phosphor pattern resin composition, a partition wall pattern resin composition, and a cured product thereof.

  The resin composition of the present invention is excellent in developability in pattern formation of resistors, phosphors, barrier ribs or conductor circuits by selectively exposing with ultraviolet rays through a film having a pattern formed and developing an unexposed portion. The pattern accuracy after development is good, and even when baked at a low temperature, the organic matter remains little and the adhesion is excellent.

  Hereinafter, the present invention will be described in detail. The polymer (A) used in the present invention will be described in the case of using a known polymerization method, for example, solution polymerization obtained by solution polymerization or emulsion polymerization. The unsaturated monomer mixture is polymerized by adding a polymerization initiator in an applicable organic solvent and heating and stirring the mixture in a nitrogen stream, preferably at 50 ° C to 100 ° C. Examples of the organic solvent include alcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, and ethylene glycol; ketones such as methyl ethyl ketone and cyclohexanone; and aromatic hydrocarbons such as toluene and xylene. Cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, propylene glycol alkyl ethers such as propylene glycol methyl ether, polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether, ethyl acetate, acetic acid Acetates such as butyl, cellosolve acetate, propylene glycol monomethyl acetate, lactates such as ethyl lactate and butyl lactate, Alkyl glycol ethers. 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.

  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) acrylate Examples include polyethylene glycol mono (meth) acrylate such as methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and alkoxy polyethylene glycol (meth) acrylate such as methoxytetraethylene glycol mono (meth) acrylate. . These ethylenically unsaturated monomers and glycerol mono (meth) acrylate can be used alone or in combination.

  Component (a) is 30% by weight or more, particularly preferably 50% by weight based on the total amount of unsaturated monomers used in the polymer (A) for the purpose of improving the water solubility of the polymer (A) component of the present invention. % Or more is desirable. The molecular weight of the polymer (A) is preferably 10,000 to 200,000.

  Specific examples of the component (b) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, ( Examples include meth) acrylic acid, (meth) acrylamide, N-methyl (meth) acrylamide, and styrene.

In the present invention, the 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, and acryloyl. Morpholine, hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polybasic acid anhydride (for example, Succinic acid, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) half-ester, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tri Methylolup Pantri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, and di (meth) acrylate of ε-caprolactone adduct of neopent glycol hydroxybivalate (eg Nippon Kayaku) KAYARAD HX-220, HX-62, etc.), pentaerythritol tetra (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, poly (meth) acrylate, 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, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxypolyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether) and (meth) acrylic acid Reactive diluent (B-1) such as epoxy (meth) acrylate as a reactant, 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, acetate esters, acetate acetate Esters such as toluene, 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, γ- Examples thereof include organic solvents (B-2) such as butyrolactone and solvent naphtha.

  Specific examples of the photopolymerization initiator (C) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane. -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide , Michler's ketone, benzyldimethylketanol, 2-ethylanthraquinone and the like. Further, a photopolymerization accelerator (for example, amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester) as a promoter of these photopolymerization initiators (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, praseodymium oxide, oxidation, preferably having a particle size of 10 μm or less. Metal oxide or mixture of neodymium, 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 gold powder, lanthanum , Cerium, samarium, praseodymium, neodymium, promethium, europium, gadolinium, terbium, dysprosium, holmium, thulium, erbium, matenium, yttrium, scandium, etc., metal powder, glass powder, glass bi Can be exemplified's like. Due to the characteristics of these, it 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 can be prepared by dissolving, mixing and kneading the components (A), (B), (C) and (D). In the resin composition of the present invention, the proportion of each component used 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. The component (D) is preferably 45 to 95%, particularly preferably 50 to 90%, in the composition. The preferable usage amount of each component in the total amount of (A) + (B-1) + (C) is as follows. That is, the amount of component (A) used is 30 to 90%, the amount of component (B-1) used is 5 to 65%, and the amount of component (C) used is 5 to 30%. The usage-amount of an organic solvent (B-2) can be used in arbitrary ratios for the objectives, such as viscosity adjustment suitable for using the composition of this invention.

  The resin composition of the present invention includes a leveling agent, an antifoaming agent, a polymerization inhibitor, a wax, a non-reactive polymer (for example, polyethylene glycol, polyethylene glycol and a polybasic acid, or an anhydrous acid thereof as long as the performance is not impaired. Polyester, acrylic polymer, etc., which are a reaction product with an acid, etc., etc. can also be used.

As described above, the resin composition of the present invention can be used as a resistor composition, a phosphor resin composition, a partition resin composition, and a conductor circuit resin composition. It is applied on the entire surface of various substrates (for example, glass, ceramic, etc.) by a method such as curtain flow coating or spray coating. After coating, if necessary, the organic solvent was removed by pre-baking at about 50 to 250 ° C. with far infrared rays or warm air, and then ultraviolet rays were exposed using a negative mask in which only the portion to be patterned was allowed to pass ultraviolet rays. The exposure amount of ultraviolet rays is preferably 100 to 5000 mJ / cm ² . Next, using a dilute alkaline aqueous solution (for example, 1.5% sodium carbonate aqueous solution, 1% caustic aqueous solution) or a water developer, development is performed by means such as spraying, followed by baking at 400 to 1000 ° C. for example. Form.

The present invention will be described below with reference to Examples 1 to 4. In the examples, parts represent parts by weight. Resistor resin compositions were prepared according to the compositions shown in Table 1. The obtained resin composition was applied to the entire surface of the glass substrate with a 150 mesh polyester screen with a film thickness of 35 μm (dry film thickness), pre-baked at 80 ° C. for 30 minutes, and then contacted with a negative film to obtain an ultrahigh pressure. 150 mJ / cm ^{2 was} irradiated with a mercury lamp, and the unexposed area was developed with water (40 ° C.) at a spray pressure of 2 kg / cm ² for 2 minutes. After development, the resist pattern was formed by baking in air at 700 ° C. for 15 minutes. Residual resin content in the pattern, developability, the state of the pattern after development, and adhesion to the glass substrate after firing were evaluated.

(Synthesis example of polymer (A))
Synthesis example 1
70 parts of glycerol methacrylate, 30 parts of methyl methacrylate, 100 parts of carbitol acetate and 3 parts of benzoyl peroxide were added, heated in a nitrogen stream, polymerized at 75 ° C. for 5 hours, and 50% polymer (A-1 ) A solution was obtained. The average molecular weight of the polymer (A-1) was about 100,000.

Synthesis example 2
Add 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, heat in a nitrogen stream, and polymerize at 75 ° C. for 5 hours. And a 50% polymer (A-2) solution was obtained. The average molecular weight of the polymer (A-2) was about 50,000.

Synthesis example 3
70 parts of methoxytetraethylene glycol monomethacrylate, 30 parts of methyl methacrylate, 100 parts of carbitol acetate and 3 parts of benzoyl peroxide are added, heated under a nitrogen stream, polymerized at 75 ° C. for 5 hours, and 50% polymer (A -3) A solution was obtained. The average molecular weight of the polymer (A-3) was about 150,000.

Table 1
Example
1 2 3 4
Polymer (A-1) obtained in Synthesis Example 1 16 12
Polymer (A-2) obtained in Synthesis Example 2 16
Polymer (A-3) obtained in Synthesis Example 3 14
Diacrylate of tetraethylene glycol diglycidyl ether 2 2 11 8
KAYARAD PEG400DA * 1 7 5
KAYARAD DPHA * 2 2 2
KAYACURE DETX-S * 3 2 2 2 2
KAYACURE EPA * 4 2 2 2 2
Ruthenium oxide powder 30 30 30 30
Glass beads 30 30 30 30
Propylene glycol monomethyl ether acetate 37 37 39 38
Residual organic matter (wt%) 0.2 0.3 0.1 0.15
Developability ○ ○ ○ ○
Pattern status after development ○ ○ ○ ○
Adhesiveness ○ ○ ○ ○

* 1 KAYARAD PEG400DA: Nippon Kayaku Co., Ltd., Polyethylene Glycol Diacrylate * 2 KAYARAD DPHA: Nippon Kayaku Co., Ltd., Dipentaerythritol Penta and Hexaacrylate Mixture * 3 KAYACURE DETX-S: Nippon Kayaku ( 2,4-diethylthioxanthone, photopolymerization initiator * 4 KAYACURE EPA: Nippon Kayaku Co., Ltd., p-dimethylaminobenzoic acid ethyl ester

(Residual organic content): Measured weight loss after baking at 700 ° C.

(Developability): A 1.5% sodium carbonate aqueous solution was developed at a liquid temperature of 40 ° C. for 2 minutes at a spray pressure of 2 kg / cm ² and evaluated as follows.
○ ···· Complete development.
Δ: There is a slight residue.
× ··· Some parts are not developed.

(State of pattern after development):
○ The pattern is maintained accurately.
Δ: The width of the pattern is narrow.
× ··· A part or all of the pattern part is peeled off.

(Adhesion): A cellophane (registered trademark) peel test was performed.
○ ・ ・ ・ ・ No peeling at all.
Δ ···· Partly peeled off.
× ··· There are many peeled parts.

  As is apparent from the results in Table 1, the resin composition of the present invention and the cured product thereof have excellent developability, good pattern accuracy after development, little residual organic matter after baking, and excellent adhesion. Yes.

Claims (2)

General formula (1)

(Wherein R ₁ is hydrogen or a methyl group, R ₂ is hydrogen or a C _{1 to} C ₅ alkyl group, and n is an integer of 1 to 10) and Obtained by polymerizing 30% by weight or more of glycerol mono (meth) acrylate (a) and 70% by weight or less of ethylenically unsaturated monomer (b) copolymerizable with component (a) other than component (a) Selected from polymer (A), diluent (B), photopolymerization initiator (C), metal powder, metal oxide or glass (D) (however, silver-copper A resin composition for a phosphor pattern characterized by containing an alloy powder). A cured product of the composition according to claim 1.