JPH09194548A - Resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which contains a specific (meth)acrylate reaction product, a diluent, a photopolymerization initiator and a metallic powder and is useful for resister pattern because it shows excellent pattern accuracy after pattern development, reduced residue of organic substance after heating and firing and excellent adhesion. SOLUTION: This resin composition comprises (A) a reaction product between (iv) a (meth)acrylate bearing one hydroxyl group and a copolymer prepared by polymerization of (i) an ethylenically unsaturated monomer of the formula (R1 is H, methyl; R2 is H, an alkyl; n is 2-30) and/or glycerol mono(meth) acrylate, (ii) a compound bearing a (meth)acryloyl group or a vinyl group and an isocyanate group, respectively, (iii) other copolymerizable ethylenically unsaturated monomers than the compounds (i) and (ii) as an arbitrary component, (B) a diluent such as 2-hydroxyethyl (meth)acrylate, (C) a photo-polymerization initiator, for example, 2,4-diethylthioxanthone and (D) one, two or more kinds selected from metal powder, metal oxide or glass.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resistor pattern used in plasma displays, fluorescent display tubes, electronic parts, etc.
It is preferably used in the manufacturing process of conductor circuit patterns, phosphor patterns, partition walls, etc., and is exposed to ultraviolet rays,
400-100 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 0 ° C., a cured product thereof, and firing. Regarding molded products.

[0002]

2. Description of the Related Art Conventionally, resistors, phosphors and partition walls for plasma displays or fluorescent display tubes, or conductors for circuits have been formed by resistor paste (resistor in paste form), phosphor paste (fluorescence). The body is made into a paste), the partition wall paste (a partition material is made into a paste) and the conductor paste (a conductive material such as copper powder and silver powder is made into a paste) are pattern-printed by screen printing, etc., and then It is known to form a resistor pattern, a phosphor pattern and a partition pattern, or a conductor circuit pattern by firing. 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 a 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 isocyanate group in one molecule, copolymerization other than the components (a) and (b) as an optional component Reaction product (A) of polymer (d) obtained by polymerizing possible ethylenically unsaturated monomer (c) and (meth) acrylate having one hydroxyl group, diluent (B), initiation of photopolymerization Agent (C), metal powder,
A resin composition containing one or more kinds (D) selected from metal oxides and glasses,
[2] The resin composition according to the above [1] for a resistor pattern, a conductor pattern, a phosphor pattern or a partition pattern,
[3] A cured product of the composition according to the above [1] and [2],
[4] A resistor, a conductor, a phosphor, and a partition obtained by firing the cured product according to the above [3].

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the present invention, a reaction product (A) of the polymer (d) and a (meth) acrylate having one hydroxyl 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, the above (a),
Polymerization of an ethylenically unsaturated monomer mixture comprising components (b) and (c) by adding a polymerization initiator in an applicable organic solvent and heating and stirring under a nitrogen stream at preferably 50 to 100 ° C. Let 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 butyl cellosolve, carbitols such as carbitol and butyl carbitol, propylene glycol alkyl ethers such as propylene glycol methyl ether, polypyropyrene glycol alkyl ethers such as dipropylene glycol methyl ether, ethyl acetate , Butyl acetate, cellosolve acetate, acetic acid esters such as propylene glycol monomethyl acetate,
Lactic acid esters such as ethyl lactate and butyl lactate, dialkyl glycol ethers and the like can be mentioned. 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. The weight (d) has a molecular weight of about 1
0000-200000 is preferable.

Examples of the component (b) include methacryloyloxyethyl isocyanate and m-isopropenyl-α, α-dimethylbenzyl isocyanate.
The component (b) is used in the polymer (d) (a), (b).
And 10 to 70% by weight, and particularly preferably 20 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.

0.5% of hydroxyethyl (or hydroxypropyl) (meth) acrylate or the like is added to 1 equivalent of the isocyanate group of the polymer (d) thus obtained.
It is preferred to react ~ 1.1 equivalents. In order to accelerate the reaction, it is preferable to add dibutyltin dilaurate or the like as a reaction catalyst in the reaction solution in an amount of 0.1 to 1%. During the reaction, a polymerization inhibitor (eg, methoxyphenol, methylhydroquinone, hydroquinone, phenothiazine, etc.) is added to the reaction solution in an amount of 0.05 to 0.5 to prevent polymerization.
% Is preferably added. The reaction temperature is 90 to 150.
The temperature and reaction time are preferably 5 to 70 hours.

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 Mention may be made of glass beads 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, 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
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.

[0020]

EXAMPLES The present invention will be described below with reference to Examples 1-8. In the examples, “parts” means “parts by weight”. Resin compositions for resistors were prepared according to the compositions shown in Tables 1 and 2 below. 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 at 00 mJ / cm ² and then spray the unexposed area with 1% aqueous sodium hydrogen carbonate solution or water (40 ° C) at a spray pressure of 2 kg.
Development was carried out at / cm ² for 2 minutes. After development, in air, 450-60
Baking was performed at 0 ° 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 methacryloyloxyethyl isocyanate, 100 parts of carbitol acetate and 3 parts of benzoyl peroxide were added,
It heated under nitrogen stream and superposed | polymerized at 75 degreeC for 5 hours, and obtained the 50% polymer (d-1) solution. Next, 300 parts of this 50% polymer (d-1) solution, 37.6 parts of hydroxyethyl acrylate, and methyl hydroquinone of 0.1.
16 parts and 0.9 parts of dibutyltin dilaurate were mixed and dissolved, and reacted at 95 ° C. for 32 hours to obtain a reaction product (A-1) solution (solid content 55.6%). The average molecular weight of the reaction product (A-1) was about 120,000.

Synthesis Example 2 50 parts of tetraethylene glycol monomethacrylate,
25 parts of methacryloyloxyethyl isocyanate, 25 parts of methyl methacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 2 parts of azobisisobutyronitrile were added and 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, this 50% polymer (d-1) solution 30
0 parts, 35.1 parts of hydroxypropyl acrylate, 0.16 parts of methylhydroquinone, and 0.9 parts of dibutyltin dilaurate were mixed and dissolved, and reacted at 95 ° C. for 32 hours to prepare a solution (A-2) (solid content 55. 2%) was obtained. The average molecular weight of the reaction product (A-2) was about 80,000.

Synthesis Example 3 Methoxynonaethylene glycol monomethacrylate 5
0 parts, methacryloyloxyethyl isocyanate 20
Parts, 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.
% Polymer (d-3) solution was obtained. Next, 300 parts of this 50% polymer (d-3) solution, 25.0 parts of hydroxyethyl acrylate, 0.16 parts of methylhydroquinone,
Mix and dissolve 0.9 parts of dibutyltin dilaurate to give 9
The reaction was carried out at 5 ° C for 32 hours to obtain a reaction product (A-3) solution (solid content 53.8%). The average molecular weight of the reaction product (A-3) was about 170,000.

[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 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 (1% sodium hydrogen carbonate solution) ○ ○ ○ ○ Pattern condition after development ○ ○ ○ ○ Adhesion ○ ○ ○ ○

[0025]

[Table 1] Table 2 Example 5 6 7 8 Polymer solution (A-1) 11 obtained in Synthesis Example 1 Polymer solution (A-2) 11 obtained in Synthesis Example 2 Weight obtained in Synthesis Example 3 Combined solution (A-3) 1 16 Irg-651 * 5 0.3 0.3 0.3 0.15 Phosphor powder 30 30 30 30 Residual organic matter (wt%) 0.2 0.3 0.1 0.15 Developability (water) ○ ○ ○ ○ Pattern state after development ○ ○ ○ ○ 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

(Residual organic content): Measure 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.

[0029]

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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 3/10 C08K 3/10 3/40 3/40 C08L 33/14 LHU C08L 33/14 LHU G03F 7/027 502 G03F 7/027 502

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 isocyanate group in one molecule, and (a) and (b) as optional components
Copolymerizable ethylenically unsaturated monomer other than the components (c)
Reaction product (A) of polymer (d) obtained by polymerizing (D) and (meth) acrylate having one hydroxyl group, diluent (B), photopolymerization initiator (C), metal powder, metal oxide or glass A resin composition containing one or more kinds (D) selected from the above. 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.