JPH0395281A - Solder resist ink composition and its cured product - Google Patents

Abstract

PURPOSE:To obtain an ink with excellent heat resistance, electric insulation characteristics, adhesive properties, moisture resistance and chem. resistance, high heat distortion temp. and hardness and little bleeding by compounding a solder resist ink compsn. with a specified epoxy resin. CONSTITUTION:A solder resist ink compsn. count. an epoxy resin (A) of the formula, which can be easily available in the market ant e.g. a commercially available product with an epoxy equivalent of 210 and a softening point of 59 deg.C etc., can be cited. As a curing agent (B), dicyandiamide, imidazole compd., arom. amine compd. and photo-cationic polymn. catalysts are cited. In addition, as a solvent (C), ethyl cellosolve, isopropyl cellosolve. carbitol acetate, etc., are cited. The of components (A)-(C) to be used are pref. 0.5-60 pts.wt. component (B) and 20-60 pts.wt. component (C) based on 100 pts.wt. component (A).

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides an adhesive that has excellent heat resistance, electrical insulation, adhesion, moisture resistance, chemical resistance, high heat distortion temperature, hardness, and low bleeding. The present invention relates to a resist ink composition and a cured product.

(Prior Art) Solder resist ink is usually used to form a desired circuit by etching a circuit board (for example, a copper-clad laminate made of an organic material such as paper-phenol, paper-epoxy, glass-epoxy, etc.). Screen printing is applied to the surface of a printed circuit board obtained by forming a printed circuit board, or a circuit board obtained by forming a desired circuit with conductors, resistors, etc. using a screen printing method using an inorganic material such as ceramic as a base material. A protective film is formed by coating or roll coating, and is used to protect electrical and moisture-resistant circuits, protect circuits during soldering, and protect circuit boards during plating processes. 1977
-87028, JP 54-156167, JP 55-22175, JP 55-53478, JP 55-46165, JP 61-12772, and JP 63-30578 No. etc.). As a solder resist, a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolac type epoxy resin mixed with a curing agent is conventionally used.

(Problem to be solved by the invention) In recent years, circuit boards have become smaller and more dense, and along with this, the characteristics required for solder resists have also become more sophisticated. There is a growing demand for materials with better electrical insulation, moisture resistance, etc.

(Means for Solving the Problems) The present invention has high heat distortion temperature, excellent heat resistance, electrical insulation, adhesion, hardness, moisture resistance, chemical resistance, plating resistance, etc.
Another object of the present invention is to provide a solder resist ink set with less bleeding.

That is, the present invention has the following features: 1. A solder resist ink composition containing an epoxy resin (A) represented by formula [I].

2. 1. A sonoreder resist 1/ink composition comprising the epoxy resin (A) according to item 1, a curing agent (B), and a solvent (q).

3. 3. The solder resist ink composition according to item 2, wherein the curing agent (8) is one or more of dicyandiamide, an imidazole compound, a triazine compound, a urea compound, an aromatic amine compound, and a photocationic polymerization catalyst.

4. Solvent (as Q, general formula [■] R+ + O R2 9n OR3Cn] (in the formula, R
1 is H or an alkyl group having 1 to 8 carbon atoms, R2 is substituted with a methyl group, and ru is an alkyl group having 1 to 8 carbon atoms, provided that R+ and ru are not H at the same time. n is 1
Indicates an integer of ~4. ) and one or more solvent naphthas.

5. A cured product of the solder resist ink composition according to item 1, item 2, or item 3.

6. A cured product of the solder resist 1/ink composition according to item 4.

Regarding.

The epoxy resin (A) represented by the formula [■] can be easily produced manually from the market. For example, Mitsui Petrochemical Industries f.
l'l) TECHMORE VG-3 1 0 1,
! Examples include a phoxy equivalent of 210 and a softening point of 59°C. The cured product (.B) used in the present invention is a dicyandiamide, imidazole compound (for example, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-
Ethyl-4-methylimidazole, 2,4-diamino-6-{2-methylimidazole (e.g., triphenylsulfonium hexasolyl(l)}monoethyl-S-
IJ azine, 2,4 fluorophosphate,
Triphenylsulfonydiamino-6-(2-ethyl-
4-Methylium hexafluorophosphate, triphenylimidazo (1) monoethyl-8-}riazine-i
Rusulfonium hexafluoroantimonate, socyanur a adduct, 2-methyl-imidazole triphenylselenium hexafluorophosfur, 1-ph2-2-methyl-imitasol ate, triphenylselenium hexafluoro2- phenyl-4-methyl-
5-hydroxymeroantimonate, diphenyliodonium hethylimidazole, etc.), triazine compounds (e.g.
Donium hexafluorophosphate, 2,4-azine-yne cyanuric acid adduct, 2-1:'Ni-cyclobentadien-1-yl)C(1-methy4,6-diamino-S-}riazine, 2- methoxyethyl)-benzene)-Fe-hexafluoroethyl-4,6-diamino-S-triazine, phosphate (manufactured by Ciba Geigy, Irugaki 2-0-cyanophenyl-4,6-
diamino-S-Ar261), etc.).

Particularly preferred curing agents (8) used in the present invention are -(3.
4-dichlorophenyl) - 1. 1'-dimethy
Examples include dicyandiamide, 2,4-diamylurea, 1,1-isophorone-bis(3-methino-6-
[2-methylimidazolyl(15:l-eru-3-
Hydroxyethyl urea), 1.1-} Chiru S
monotriazine, 2-ethyl-4-methylylene bis(3
．． 3-dimethylurea), etc.), limidazole,
1.1'-isophorone-bis (3 aromatic amine compound (
For example, 4,4-diamino-methyl-3-hydroxyethylurea), 1-diphenylmethane, etc.) and photocationic polymerization catalyst 1'-tolylene-bis(3,3-dimethylurea)-3-(3,4-dichlorophenyl)-1
．． 1-Dime Extender pigments such as magnesium oxide, aerodyltyl urea, and photocationic polymerization catalysts are commercially available products, such as chicken trobby agents such as silicone and acrylic, manufactured by Asahi Denka ■, SP-150, SP-170, etc. Examples include leveling agents, antifoaming agents, and flame retardants such as copolymers. Agents, colorants, etc. can be added. Solvents (Q) used in the present invention include: These various additives can be added to the composition in arbitrary amounts, such as ethyl cellosolve, isoprobyl cellosolve, and novolac. It is also possible to add acetate, ethyl rubitol, butyl cal, etc. type eptyl cellosolve, diethylene glycol monoboxy resin, Bisfu-based resin, etc.

In the general use of the composition of the present invention, vitol, cellosolve acetate, butyl serate, sorp acetate, carbitol acetate, and the composition of the present invention are printed on a substrate by screen printing with bilene glycol monomethyl ether, and then Heat curing (13
0-170°C) and solvent naphtha. By using the present invention, a protective film can be formed on a base material.

When using a cationic polymerization catalyst for each curing agent used in the solder resist ink composition, minutes (A) to (
The proportion of Q used is 100 parts by weight of component (A), and it is necessary to irradiate it with ultraviolet rays before heat curing.

When the component (B) is 0. 5 to 60 parts by weight is preferred (Example), particularly preferably 1 to 30 parts by weight, (
The Q component is preferably 20 to 60 parts by weight, particularly preferably 20 to 60 parts by weight, which will specifically explain the present invention with examples.
Ru. The numbers t and t in the examples represent parts by weight.

Q is 30 to 50 parts by weight Examples 1 to 3, Comparative Examples 1 to 4. The composition of the present invention is further blended with various additives according to the composition shown in Table 1, for example, talc, silica, alumina, barium sulfate, and kneaded using a roll to form a solder resist ink composition. Prepared. This ink composition was applied to a printed wiring board by screen printing to a film thickness of approximately 25 μm, and was cured by heating at 150° C. for 30 minutes to obtain a printed wiring board having a protective film. Various performance tests were conducted on the obtained protective film of the printed wiring board. These results are shown in Table 1.

[Toluene solubility of ink composition]: 5 g of ink composition
Dissolve in 50g of toluene.

○・・・・・・Dissolution Δ・・・Semi-dissolved ×・・・・・・Insoluble [Evaluation of physical properties of protective film] (Pencil hardness): Measured according to JIS-K-5400.

(Adhesion, properties): Grid test according to JIS-D-0202.

(Heat resistance) The state of the coating film after being immersed in molten solder at 8260° C. for 180 seconds was evaluated.

○...No abnormality at all.

×・・・Discoloration, peeling, and blistering.

(Gold plating resistance) Manufactured by Fukamimura Kogyo ■, Allna 533 conditions, IA/dm, 15 minutes, plating thickness, 2 μm.

O...No abnormality at all.

×・・・Discoloration, peeling, and blistering.

(Acid resistance): 10Vol%H2SO. in aqueous solution,
The state of the coating film after 1-immersion at room temperature was evaluated.

◎・・・・・・No abnormality after 48 hours.

○・・・No abnormalities for up to 24 hours.

△・・・No abnormalities for up to 8 hours.

×・・・Peeling and blisters occur in 1 hour.

(Alkali resistance): The state of the coating film after being immersed in a 10 wt% NaOH aqueous solution at room temperature was evaluated.

○: Abnormal for up to 30 days.

△・・・Abnormal for up to 15 days.

×・・・Peeling and blisters occur within 7 days.

(Heat distortion temperature) H TMA method, Shimadzu thermal analyzer TMA
-40.

(Electrical insulation resistance): Measured according to JIS-Z-3197.

(Bleed): Width of the pleat of an ink set (μm)
Measure.

(Discoloration of protective film during heat curing of ink composition): The state of discoloration of the protective film during heat curing (150° C., 60 minutes) was evaluated.

○...It's completely abnormal.

△...Discoloration.

×... Severe discoloration.

Note +1) VG-3 1 0 1...Mitsui Petrochemical Industries ■, epoxy resin, compound represented by formula [I].

-x2) Epicoat 828/Curved/Oilized Shell Epoxy■
, Bisphenol A epoxy resin *3) Ebicoat 1001...-X4)
YDN-1 8 0...Toto Kasei ■, phenol novolac type epoxy resin 45) EOCN-102...Nippon Kayaku ■, cresol novolac type epoxy resin -%6) EPPN-201. ... Nippon Kayaku■,
Phenol novolac type epoxy resin-%7) SP-1. 7 0... Minister of Asahi Denka,
Photocationic polymerization catalyst Example 3 was prepared by applying the ink composition to a printed wiring board by screen printing, drying at 80°C for 30 minutes, irradiating with ultraviolet light (500 mJ/cm"), and then applying the ink composition to a printed wiring board by screen printing.
The protective film of the printed wiring board obtained by heat curing at 50° C. for 30 minutes was also tested for performance.

1) Manufactured by Toshiba Silicon ■, antifoaming agent Example 4. In Example 1, 8.5 parts of dicyandiamide, 3-(3 .4-dichlorophenyl) - 1. When a solder resist ink composition was prepared using 6.0 parts of 1'-dimethylurea and an experiment was conducted, similar results were obtained.

Example 5. In Example 1, KAYAHARD A-S (Nippon Kayaku Co., Ltd. ft.
! ! A solder resist ink composition was prepared using 30 parts of Aromatic Amine-based Epoxy Curing Agent (Aromatic Amine-based Epoxy Curing Agent) manufactured by A.S.

(Effects of the Invention) The cured film of the solder resist ink composition of the present invention has a high heat distortion temperature, and also has excellent heat resistance, moisture resistance, high hardness, plating resistance, chemical resistance, and electrical insulation properties. It has excellent characteristics and also has less bleed.

Claims (1)

[Claims] 1. Epoxy resin (A) represented by formula [I]▲mathematical formula,
There are chemical formulas, tables, etc.▼Solder resist ink composition containing [I]. 2. A solder resist ink composition comprising the epoxy resin (A) according to item 1, a curing agent (B), and a solvent (C). 3. The solder resist ink composition according to item 2, wherein the curing agent (B) is one or more of dicyandiamide, an imidazole compound, a triazine compound, a urea compound, an aromatic amine compound, and a photocationic polymerization catalyst. 4. As the solvent (C), use the general formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, R_1 is H or an alkyl group having 1 to 8 carbon atoms, R
_2 is an ethylene group which may be substituted with a methyl group, R_3 is H or ▲a numerical formula, chemical formula, table, etc.▼; R_4 is an alkyl group having 1 to 8 carbon atoms, provided that R_
1 and R_3 are never H at the same time. n is 1 to 4
indicates an integer. ) The solder resist ink composition according to item 2 or 3, which uses one or more of solvent naphtha and a compound represented by formula (2). 5. A cured product of the solder resist ink composition according to item 1, item 2, or item 3. 6. A cured product of the solder resist ink composition according to item 4.