JPH06332169A - Resist ink composition - Google Patents

Abstract

PURPOSE:To obtain the resist ink composition functioning as a solder resist film superior in a water-soluble flux resistance and high in reliability by using an unsaturated compound obtained by reaction between an epoxy compound having a naphthalene skeleton and an unsaturated monobasic acid. CONSTITUTION:This resist ink composition contains (A) the unsaturated compound obtained by reaction between the 1, 6-diglyidyl-oxynaphthalene and the unsaturated monobasic acid, (B) an active light setting resin obtained by reaction between the reaction product (of an epoxy compound with an unsaturated monobasic acid) and a saturated or unsaturated polybasic acid, (C) a photopolymerization initiator, and (D) an epoxy compound having >=2 epoxy groups in one molecule in a mixing weight ratio A/B of 5-30:95-70 and in that C/(A+B) of (2-30):100 and in that D/B of (10-50)/100, thus permitting this composition to be improved in photosensitivity and easily photo setting in a short exposure time and easily developed with a weak alkali aqueous solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist ink composition which is preferably used as a solder resist, especially a water-soluble flux resistant resist in a manufacturing process of a printed wiring board.

[0002]

2. Description of the Related Art Conventionally, in the printed wiring board industry,
A resist ink composition having excellent properties that can be used as a solder resist, a resist for chemical plating, etc. is known. The main purpose of solder resist is to limit the solder area during soldering, prevent solder bridging, prevent corrosion of bare copper conductor, and maintain electrical insulation between conductors for a long time. . When forming a solder resist film on a printed wiring board, conventionally, a thermosetting resist ink containing epoxy resin, aminoplast or the like as a main component was printed by a screen printing method to thermoset the transfer portion. However, in recent years, as electronic components such as ICs, LSIs, and VLSIs have become highly integrated, the printed wiring boards on which these are mounted are also becoming more and more dense. At present, a surface mounting method (SMT) for mounting an LSI component such as a flat plastic package (FPP) on the surface of a substrate is adopted, and the conventional method cannot meet the demand for high density. It's gone.

Therefore, a method for obtaining a solder resist film by utilizing the principle of photography has been developed, and along with this, development of a photo solder resist ink has been studied.
For example, Japanese Patent Application Laid-Open No. 61-272 discloses a composition containing a novolac type epoxy acrylate containing an epoxy group and a photopolymerizable initiator as main components. These compositions are also excellent in heat resistance and useful, but it is necessary to use a 1,1,1-trichloroethane / lower alcohol mixed solution as a developing solution, and there is a problem in developing solution management.
In addition, the use of 1,1,1-trichloroethane is not preferable in terms of environmental protection because it may cause groundwater contamination.

In view of the working environment and processing cost, a photo solder resist ink has been proposed which can be developed with a weak alkaline aqueous solution such as an aqueous solution of sodium carbonate, instead of the type developed with an organic solvent. There is. For example, JP-A-61-243869 and JP-A-63-278052 contain a resin component having a novolac type or bisphenol type epoxy resin skeleton, can be developed with a weak alkaline aqueous solution, and have heat resistance, A permanent protection mask type resist ink composition having excellent chemical resistance and the like is disclosed. Further, JP-A-62-158710 and JP-A-62-285903.
JP-A No. 63-11930 and JP-A No. 63-11930 disclose an alkali-developable resist ink composition comprising a copolymer of maleic anhydride and styrene with a ring-opening addition of hydroxyalkylene (meth) acrylate as a base polymer. It is disclosed.

Furthermore, in recent years, the use of CFCs, which are the cause of ozone layer depletion, has been severely restricted, and it has been desired to manufacture printed wiring boards without a CFC cleaning step. For this reason, various highly safe cleaning agents have been tried in place of CFCs, but these are not yet satisfactory in terms of cleaning effect and cost. On the other hand, when soldering components to a printed wiring board, by replacing the conventionally used rosin-based flux with a specific water-soluble flux, it is possible to safely remove the flux without using CFCs or other cleaning agents. Attempts have been made to produce a printed wiring board that can be cleaned and removed, and the effect has been considerable.

[0006]

However, when a solder resist film is formed by a photographic method using the above resist ink composition, acid resistance, alkali resistance, solvent resistance, solder heat resistance and water solubility Flux resistance is not sufficient, and a product having satisfactory performance for use as a permanent protection mask for a printed wiring board has not been obtained. Then, this invention aims at providing a resist ink composition which does not have such a problem. That is, a resist ink that has good sensitivity to light, can be easily photocured in a short exposure time, can be easily developed with a weak alkaline aqueous solution such as sodium carbonate, and can be cured not only by light but also by heat. The composition is a high reliability solder that is excellent in acid resistance, alkali resistance, solvent resistance, solder heat resistance, and water-soluble flux resistance after the composition is coated on the object and then cured by light and heat. It is intended to provide a resist ink composition that functions as a resist film.

[0007]

Means for Solving the Problems As a result of earnest studies to solve such problems, the inventors have found that an unsaturated compound obtained by reacting an epoxy compound having a naphthalene skeleton with an unsaturated monobasic acid. The present invention has been achieved by finding that the above-mentioned problems can be achieved by using a compound. That is, the present invention relates to (A) an unsaturated compound obtained by reacting 1,6-diglycidyloxynaphthalene with an unsaturated monobasic acid, and (B) a reaction product of an epoxy compound and an unsaturated monobasic acid. Containing an actinic ray-curable resin obtained by reacting with a saturated or unsaturated polybasic acid anhydride, (C) a photopolymerization initiator, and (D) an epoxy compound having two or more epoxy groups in one molecule. The mixing ratio of the unsaturated compound (A) and the actinic ray-curable resin (B) is 5 to 30:95 to 70 by weight, and the photopolymerization initiator (C) is added to the unsaturated compound (A). 2 to 30 parts by weight with respect to 100 parts by weight of the mixture of an actinic ray-curable resin (B) and 10 to 50 parts by weight of the epoxy compound (D) with respect to 100 parts by weight of the actinic ray-curable resin (B). A resist ink composition characterized by It is intended. (Hereinafter, the unsaturated compound (A), the actinic ray curable resin (B), the photopolymerization initiator (C) and the epoxy compound (D) are respectively the component A and the component B).
It is abbreviated as component, C component and D component. )

The present invention will be described in detail below. The resist ink composition according to the present invention has 1,6-
The molar ratio of diglycidyloxynaphthalene and unsaturated monobasic acid of carboxylic acid group / epoxy group is, for example, 0.8 to
It contains an unsaturated compound obtained by addition reaction in the range of 1.1. 1,6-Diglycidyloxynaphthalene is a known compound, and as a commercially available product, for example, EX4032 (epoxy equivalent 14 by Dainippon Ink and Chemicals, Inc.) is used.
7) can be mentioned.

As the other unsaturated monobasic acid, acrylic acid, methacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, α-cyanocinnamic acid, cinnamic acid, and general formula (1) An acrylic acid oligomer represented by: CH ₂ ═CHCOO (CH ₂ CH ₂ COO) _n H (n is an integer of 1 to 6) (1), and a reaction product of acrylic acid and caprolactone represented by the general formula (2), _{CH 2 = CHCOO (C 5 H} 10 COO) n H (n is an integer of 1 to 3) (2) or the like is used. The compounds represented by the general formulas (1) and (2) are known and commercially available,
For example, as the compound represented by the general formula (1), Toagosei Co., Ltd. Aronix M5600 (n; average 1.2 to
As the compound represented by 1.4) and the general formula (2), Aronix M5300 (n; average 2) and the like of the same company are used. These unsaturated monobasic acids can be used alone or in combination.

In the synthesis of the component A, the addition reaction of this epoxy compound with the unsaturated monobasic acid is carried out by a conventional method, but in order to prevent the presence of unreacted substances or free carboxylic acid, the carboxylic acid group / epoxy group The molar ratio is preferably in the range of 0.9 to 1.0. The addition reaction of the epoxy compound and the unsaturated monobasic acid, for example, the epoxy compound is dissolved in an inert solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, as a catalyst. , Tertiary amines such as tri-n-butylamine and diethylcyclohexylamine, and quaternary ammonium salts such as benzyltrimethylammonium chloride and benzyltriethylammonium chloride, and, if necessary, hydroquinone monomethyl ether, p as a polymerization inhibitor. -Add methoxyphenol and add 90-110
It can be obtained by reacting with stirring at ℃ for about 8 hours.

The resist ink composition according to the present invention comprises B
It contains an actinic ray-curable resin obtained by reacting a reaction product of an epoxy compound and an unsaturated monobasic acid with a saturated or unsaturated polybasic acid anhydride as a component. Such actinic ray curable resins are already known, and for example, Japanese Patent Publication No. 51-
It is described in Japanese Patent Publication No. 28677, Japanese Patent Publication No. 59-19130, Japanese Patent Publication No. 61-243869, and the like. The preferred actinic ray-curable resin is at least one epoxy resin selected from the group consisting of bisphenol type epoxy resin, orthocresol novolac type epoxy resin, phenol novolac type epoxy resin or halogenated phenol novolac type epoxy resin, and an unsaturated unsaturated resin. A secondary acid and / or residual epoxy group of an unsaturated compound obtained by addition reaction of a basic acid and a carboxylic acid group / epoxy group in a molar ratio of 0.5 to 1.0 are saturated or unsaturated. An actinic ray curable resin obtained by reacting a polybasic acid anhydride can be mentioned.

The bisphenol type epoxy resin is obtained by reacting bisphenol with epichlorohydrin by a conventional method, and is commercially available. Orthocresol novolac type, phenol novolac type,
Alternatively, the halogenated phenol novolac type epoxy resin is obtained by reacting orthocresol, phenol, halogenated phenol or the like with an aldehyde in the presence of an acid catalyst, and any of them is commercially available.

As the bisphenol type epoxy resin,
For example, manufactured by Shell Co., Epicoat 828 (epoxy equivalent 184-194), Epicoat 834 (epoxy equivalent 2
30-270), Epicoat 1001 (epoxy equivalent 4
50-500), Epicoat 1004 (epoxy equivalent 8
75-975) DER331 (epoxy equivalent 182-192), DER337 (epoxy equivalent 230-250), DER661 (epoxy equivalent 500) manufactured by Dow Chemical Co.
~ 560), DER663U (epoxy equivalent 730-8)
20) and the like.

Examples of the ortho-cresol novolak type epoxy resin include Araldite ECN1299 (softening point 99 ° C., epoxy equivalent 23
0), ECN1280 (softening point 80 ° C, epoxy equivalent 2
30), ECN1273 (softening point 73 ° C., epoxy equivalent 230) manufactured by Nippon Kayaku Co., Ltd., EOCN104 (softening point 9
0-100 ° C, epoxy equivalent 225-245), EOC
N103 (softening point 80-90 ° C, epoxy equivalent 215-
235), EOCN102 (softening point 70 to 80 ° C, epoxy equivalent 215 to 235), EOCN101 (softening point 6
5 to 69 ° C., epoxy equivalent 205 to 225) and the like.

Examples of the phenol novolac type epoxy resin include Epicoat 152 (epoxy equivalent 175) and Epicoat 154 (epoxy equivalent 176, manufactured by Shell Co.).
181), Dow Chemical Co., DEN431 (epoxy equivalent 172-179), DEN438 (epoxy equivalent 175-182), Toto Kasei Co., Ltd., YDPN-63.
8 (epoxy equivalent 170-190), YDPN-601
(Epoxy equivalent 180-220), YDPN-602
(Epoxy equivalent 180 to 220) and the like.

Examples of halogenated phenol novolac type epoxy resins include BREN manufactured by Nippon Kayaku Co., Ltd.
(Epoxy equivalent 270-300, bromine content 35-37
%, Softening point 80 to 90 ° C.) and the like, and brominated phenol novolac type epoxy resin and the like.

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, β-furylacrylic acid, β-styrylacrylic acid, α-cyanocinnamic acid, cinnamic acid, and acrylic acid represented by the general formula (1). An oligomer, a reaction product of acrylic acid represented by the general formula (2) and caprolactone, or the like is used. These unsaturated compounds alone
Alternatively, they can be used in combination.

In the synthesis of the actinic ray-curable resin of the present invention, the addition reaction between these epoxy compounds and unsaturated monobasic acid is carried out by a conventional method, but the molar ratio of carboxylic acid group / epoxy group is 0. It is preferably in the range of 0.5 to 1.0. If the molar ratio of carboxylic acid group / epoxy group is less than 0.5, the photo-cured film is likely to swell due to the development treatment after exposure, and if it exceeds 1.0, the amount of free unsaturated carboxylic acid is large. It tends to be unfavorable in terms of safety, such as increased skin irritation.

The addition reaction product of an epoxy compound and an unsaturated monobasic acid is prepared by dissolving the above-mentioned epoxy resin in an inert organic solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate or cyclohexanone, and using tri-n-as a catalyst. A tertiary amine such as butylamine or diethylcyclohexylamine, a quaternary ammonium salt such as benzyltrimethylammonium chloride or benzyltriethylammonium chloride, and hydroquinone monomethyl ether or p-methoxyphenol as a polymerization inhibitor are used at 70 to 100 ° C. It is obtained by stirring and reacting with the unsaturated monobasic acid in the above molar ratio range.

Examples of the above-mentioned saturated or unsaturated polybasic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl disubstituted butenyltetrahydrophthalic anhydride. Acid, itaconic anhydride, succinic anhydride, tricarballylic anhydride, maleic anhydride, linoleic acid adduct of maleic anhydride, chlorendic anhydride, maleic anhydride adduct of methylcyclopentadiene, anhydrous alkylated endoalkylene tetrahydro Examples thereof include phthalic acid.

The addition reaction of these polybasic acid anhydrides with the above-mentioned reaction unsaturated compound has a carboxylic acid group / hydroxyl group molar ratio of from 0.6 to 10 from the viewpoint of developability with an aqueous alkali solution and swelling of the photo-cured film. It is desirable that the range of 2.0 is carried out by a conventional method. In the portion of the reaction unsaturated compound where the epoxy group remains, the addition reaction between the carboxyl group and the epoxy group generated by the addition reaction of the polybasic acid anhydride to the secondary hydroxyl group occurs, and the resulting reaction product The carboxyl group concentration of the product decreases. Therefore, it is desirable to increase the amount of the polybasic acid anhydride used in advance so as to correspond to the decrease.

Particularly preferred actinic radiation curable resins include bisphenol type epoxy resin / acrylic acid / tetrahydrophthalic anhydride (molar ratio of acrylic acid / epoxy group = 0.5 to 1.0, tetrahydrophthalic anhydride / hydroxyl group). Molar ratio = 0.6 to 2) system resin, phenol novolac type epoxy resin / acrylic acid / tetrahydrophthalic anhydride (molar ratio of acrylic acid / epoxy group = 0.5 to 1.
0, molar ratio of tetrahydrophthalic anhydride / hydroxyl group = 0.
6-2) based resin, cresol novolac type epoxy resin / acrylic acid / tetrahydrophthalic anhydride (molar ratio of acrylic acid / epoxy group = 0.5 to 1.0, molar ratio of tetrahydrophthalic anhydride / hydroxyl group = 0. 6 to 2) based resins and the like.

The resist ink composition according to the present invention can achieve the object by mixing the component A with the component B in a specific ratio.
The weight ratio of (A) :( B) = 5 to 30:95 to 70 is preferably 10 to 20:90 to 80. The component A is a liquid compound having an unsaturated group, and when the ratio with respect to the entire composition exceeds the range of the above-mentioned (A) :( B), the drying property of the coating film in the film forming process and However, it tends to be unfavorable in terms of developability with respect to an alkaline aqueous solution.

The resist ink composition of the present invention comprises a photopolymerization initiator which produces free radicals upon irradiation with actinic rays.
That is, it contains the C component. Specific examples of the component C of the present invention include substituted or unsubstituted polynuclear quinones such as 2-
Ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc., ketoaldonyl compounds such as diacetylbenzyl, α-ketaldonyl alcohols and ethers such as benzoin,
α-hydrocarbon substituted aromatic acyloins, for example, α-phenyl-benzoin, α, α-diethoxyacetophenone, etc., benzophenone, aromatic ketones such as 4,4′-bisdialkylaminobenzophenone, 2-methylthioxanthone, Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2-ethylthioxanthone,
2-Methyl-1- [4- (methylthio) phenyl] -2
-Morpholino-propanone-1 is used, which may be used alone or in combination. The preferable amount of the component C is 100% of the mixture of the components A and B.
It is 2 to 30 parts by weight with respect to parts by weight.

The component D of the present invention contains an epoxy compound having two or more epoxy groups in one molecule. Examples of the epoxy compound include, for example, bisphenol type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, halogenated phenol novolac type epoxy resin, polyglycidyl amine type epoxy resin, triglycidyl isocyanurate, diester. Examples thereof include glycidyl biphenyl type epoxy resin and alicyclic epoxy resin. The preferable blending amount of the component D is 10 to 50 parts by weight with respect to 100 parts by weight of the component B.

In addition to the components A, B, C and D, the resist ink composition of the present invention may optionally contain a photopolymerizable unsaturated compound having at least two terminal ethylene groups. Good. Examples of the photopolymerizable unsaturated compound include trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, 1,3-butyl glycol, 1,4-butylene glycol, 1,5-pentanediol and polycaprolactone. Diol, polypropylene glycol, decamethylene glycol, glycerin, neopentyl glycol,
2,2-bis [4,4 '-(2-hydroxyethoxy)
Phenyl] propane, tris (2-hydroxyethyl)
Ester of polyhydric alcohol such as isocyanuric acid and acrylic acid or methacrylic acid, phthalic anhydride-diethylene glycol-acrylic acid (molar ratio of 1/2/2) condensate,
A low molecular weight polyester resin having an acryloyloxy group and / or a methacryloyloxy group at the terminal of a trimethylolpropane-tetrahydrophthalic acid-acrylic acid (molar ratio of 2/1/4) condensate and the like can be mentioned.

Further, the reaction products of diol monoacrylate or diol monomethacrylate and diisocyanate described in JP-B-52-43092 and the like, and diol monoacrylate described in JP-A-57-55914 and the like. It is also possible to use a / dihydric alcohol / trimethylhexamethylene diisocyanate reaction product, or an isocyanate ethyl methacrylate / water (2/1 molar ratio) reaction product.

Further, the resist ink composition according to the present invention may contain a fine particulate filler. Specific examples of the fine particulate filler include talc, silica, titanium oxide, clay, calcium carbonate, hydrous silicic acid, aluminum hydroxide, alumina, barium sulfate, antimony trioxide,
Magnesium carbonate, mica powder, aluminum silicate, magnesium silicate and the like can be used. The particle size of the fine particulate filler is preferably 0.01 to 10 μm, and more preferably 0.01 to 10 μm from the viewpoint of preventing deterioration of resolution, adhesion of the cured film and the like.
One having a thickness of 1.5 μm can be used. The fine particulate filler is preferably uniformly dispersed in the resist ink composition.

In order to increase the adhesive force between the fine particulate filler and the photopolymerizable compound, the surface of the fine particulate filler has a silane cup having a functional group such as a hydroxyl group, an amino group, an epoxy group or a vinyl group. It can also be treated with a ring agent. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, and γ-methacryloxypropyltrimethoxysilane. .

Further, the resist ink composition according to the present invention may contain other auxiliary additives. As auxiliary additives, hydroquinone monomethyl ether, polymerization inhibitors such as p-methoxyphenol, benzotriazole,
Adhesion improvers such as 5-amino-1,3,4-thiadiazole-2-thiol and 5-mercapto-1H-1,2,4-triazole, pigments such as phthalocyanine green,
Examples thereof include flame retardants such as antimony trioxide, latent curing agents for epoxy resins such as dicyandiamide and boron trifluoride / secondary amine composites. Further, for the purpose of promoting the smoothness of the coating film surface after forming the resist coating film, a leveling agent,
A defoaming agent or the like may also be contained as an auxiliary additive. This includes Monsanto's "Modaflow", Kyoeisha Yushi Co., Ltd.
"AC-300" of the company can be used.

The resist ink composition of the present invention is directly coated on a printed circuit board to be protected by a conventional method such as a dip coating method, a roll coating method, a curtain coating method and a screen printing method, and has a thickness of 10 to 150 μm. The photosensitive resist layer can be easily formed. If necessary, the composition may be dissolved in a solvent for coating. Examples of the solvent include methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate,
Cyclohexanone, methyl cellosolve, propylene glycol monomethyl ether acetate, methylene chloride,
Propylene glycol monomethyl ether etc. can be mentioned.

The exposure and development of the resist film thus formed are carried out by a conventional method. That is, the solvent is volatilized by heating and drying at the heat treatment temperature described below,
A super-high pressure mercury lamp, a high pressure mercury lamp, or the like is used as a light source, and a negative film is directly adhered to the resist film to expose it imagewise, and then the negative film is removed and developed. As the developer used in the development treatment, an aqueous alkali solution is used, and examples of the base include alkali metal phosphates such as sodium phosphate and potassium phosphate, alkali metal carbonates such as sodium carbonate, and the like. An aqueous solution of sodium carbonate is preferred.

The resist film patterned by the above method has characteristics as a corrosion resistant film for usual etching, plating, etc., but is 80 to 200 ° C. after development.
By performing the heat treatment in step 1, the properties such as adhesion, heat resistance, solvent resistance, and water-soluble flux resistance can be further improved, and a permanent protective mask satisfying the properties as a solder resist can be obtained.

[0034]

EXAMPLES The present invention will now be specifically described based on examples, but the present invention is not limited thereto. In addition, "parts" and "%" in the following examples are based on weight unless otherwise specified. The components A and B, which are parts of the compositions used in Examples and Comparative Examples, were synthesized by the following method. Component A: Synthesis of unsaturated compound solution In a three-necked flask equipped with a thermometer, a stirrer, and a condenser,
EXA4032 (Dainippon Ink and Chemicals, Inc. epoxy resin epoxide equivalent 147) 380 parts, ethyl cellosolve acetate 239 parts, N, N-dimethylbenzylamine 0.6 parts, hydroquinone monomethyl ether 0.2.
After the temperature was raised to 110 ° C. and the solution was uniformly dissolved, 177 parts of acrylic acid was added dropwise over 1 hour while maintaining the reaction temperature at 110 ° C. After the dropping, stirring was continued at 110 ° C. for 8 hours to obtain an unsaturated compound solution (component A) having a nonvolatile content of 70%. The acid value of the reaction product was 1 (KOH · mg / g) or less. Component B: Synthesis of actinic ray curable resin solution In a three-necked flask equipped with a thermometer, a stirrer, and a cooling tube,
380 parts of Epicoat 828 (bisphenol type epoxy resin manufactured by Shell Co., epoxy equivalent 190), 300 parts of propylene glycol monomethyl ether acetate,
After 0.6 part of N, N-dimethylbenzylamine and 0.2 part of hydroquinone monomethyl ether were added and the temperature was raised to 110 ° C. to uniformly dissolve them, acrylic acid was added over 1 hour while maintaining the reaction temperature at 110 ° C. 144 parts was dropped. After the dropping, stirring is continued at 110 ° C. for 10 hours to adjust the acid value of the reaction system to 1
After adjusting to (KOH · mg / g) or less, 194 parts of tetrahydrophthalic anhydride was added, and stirring was continued at 110 ° C. for about 10 hours to obtain a resin solution (component B) having a nonvolatile content of 71%. The acid value of the reaction product was 100 (KOH.mg/g).

Examples 1 to 3, Comparative Example 1 (1) Preparation of Resist Ink Composition Component A above; unsaturated compound solution (nonvolatile content 70%),
B component; actinic ray curable resin solution (nonvolatile content 71%),
And C component; benzophenone, diethylaminobenzophenone, D component; triglycidyl isocyanurate, a photopolymerizable unsaturated compound, trimethylolpropane triacrylate, fine particulate filler, barium sulfate, and as an auxiliary additive, pigment; phthalocyanine green: Epoxy resin latent curing agent; dicyandiamide, polymerization inhibitor;
Hydroquinone monomethyl ether, leveling agent / defoaming agent; Modaflow, AC-300, solvent; Propylene glycol monomethyl ether acetate were mixed in a ratio (parts by weight) shown in Table 1 and kneaded using a three-roll mill to form a resist. An ink composition was prepared.

(2) Formation of resist film The resist ink composition prepared in (1) above was applied in a thickness of 25 μm to a degreased and washed printed wiring board having a thickness of 1.6 mm, and the resist ink composition was dried in a hot air dryer at 70 μm. After drying at a temperature of 30 ° C. for 30 minutes, a negative film was adhered thereto, exposed and developed, and then heat-treated at a temperature of 140 ° C. for 50 minutes in a hot air dryer to form a pattern.

(3) Evaluation of resist film The drying property, exposure sensitivity, and developability of the coating film were tested for those dried for 30 minutes at a temperature of 70 ° C., and adhesion to a substrate, solder heat resistance, and water-soluble flux were tested. With respect to resistance, chemical resistance, solvent resistance and insulation resistance, the resist film after being exposed and developed as described above and then completely cured by heating at 140 ° C. for 50 minutes was tested.

Each evaluation was performed as shown below. (3-1) Dryability of coating film Tested according to JIS K-5400. The evaluation ranks are as follows. ◯: No tack is observed at all Δ: Slight tack is observed x: Significant tack is observed

(3-2) Exposure Sensitivity Kodak Step Tablet No. 2 (manufactured by Eastman Kodak Co., negative film with optical density steps of 0.15 and 21 steps) was adhered to the coating film, and a 5 kW ultra high pressure mercury lamp [Co., Ltd.] Oak Manufacturing Co., Ltd., HMW-201GX] is used to irradiate ultraviolet light having a wavelength of about 365 nm with an illuminance of 25 mw / cm ^2.
It is irradiated for 20 seconds (light intensity 500 mJ / cm ² ) and described later (3
The treatment was conducted in the same manner as in the developing property test for the weak alkaline aqueous solution of -3), and the number of steps of the resist film remaining on the copper foil was examined. In this evaluation method, the higher the sensitivity, the greater the number of remaining stages.

(3-3) Developability in Weak Alkaline Aqueous Solution With respect to the product subjected to the exposure treatment as in the above (3-2), a developing machine (manufactured by Yoshitani Shokai Co., Ltd.) was used using a 1% aqueous sodium carbonate solution. , YCE-85), 2.1K
Development was carried out at 30 ° C. for 60 seconds under a pressure of g / cm ² .
After the development, the product was magnified 30 times and visually inspected, and the remaining resist film was visually evaluated. The evaluation ranks are as follows. ◯: Good developability (no resist film left on the copper foil in the part shielded by the negative film) ×: Poor developability (resist on copper foil in the part shielded by the negative film) The film remains.)

(3-4) Hardness of Resist Coating The hardness of the resist coating, which was heated at 140 ° C. for 50 minutes after being exposed and developed as described in (3-2) and (3-3) above, was measured according to JIS K-5400. When a load of 1 kg was applied using a pencil hardness tester in accordance with the test method of No. 1, it was indicated as the highest hardness that the resist film was not scratched. Pencils
"Mitsubishi High Uni" (manufactured by Mitsubishi Pencil Co., Ltd.) was used.

(3-5) Adhesion with Substrate After exposing and developing as in the above (3-2) and (3-3), the resist coating film heated at 140 ° C. for 50 minutes was used.
A cross cut was inserted so that at least 100 crosses were obtained, and then a peeling test was performed using an adhesive tape, and the state of peeling of the crosses was visually evaluated. The evaluation ranks are as follows. ◯: No peeling was observed at all measuring points. Δ: Peeling was observed at 1 to 20 points among 100 measuring points. X: Peeling was observed at 21 points or more among 100 measuring points. What

(3-6) Solder heat resistance After exposing and developing as in the above (3-2) and (3-3), the resist coating which was heated at 140 ° C. for 50 minutes was attached to JIS D-0202. According to the above, the state of the resist film after the immersion was evaluated by immersing it in a solder bath at 260 ° C. for 20 seconds. The evaluation ranks are as follows. ◯: The appearance of the resist coating is normal. ×: The appearance of the resist coating is swollen, melted, and peeled.

(3-7) Water-soluble flux resistance After exposure and development as described in (3-2) and (3-3) above, the patterned substrate was heated at 140 ° C. for 50 minutes to form a water-soluble flux. Solbond No. It was immersed in K-183 (manufactured by Kenko Electronics Co., Ltd.) for 5 seconds, left in the air for 15 seconds, and then floated on the surface of the solder bath kept at 260 ° C. for 5 seconds. After that, the substrate was taken out and allowed to cool for 5 minutes, and this was treated as one cycle for 5 cycles. Then, a peeling test was performed using an adhesive tape, and the state of peeling on the copper circuit and the terminal was visually evaluated. The evaluation ranks are as follows. ◯: No peeling was observed Δ: Peeling was observed at 1 to 4 places x: Five or more peelings were observed

(3-8) Chemical resistance The resist film which has been exposed and developed as described in the above (3-2) and (3-3) and heated at 140 ° C. for 50 minutes has the following chemicals of 25 each. Immersion was performed at 0 ° C. for 1 hour, and the appearance and adhesion after immersion were evaluated. Acid resistance 10 wt% HCl aqueous solution Alkali resistance 10 wt% NaOH aqueous solution Solvent resistance 1,1,1-Trichloroethane Methylene chloride Isopropyl alcohol The evaluation ranks are as follows. ○: No abnormality ×: Dissolved or swollen

(3-9) Insulation Resistance JI was applied to the resist film which was exposed and developed as in (3-2) and (3-3) above and heated at 140 ° C. for 50 minutes.
A circular electrode was prepared according to SZ-3197, and the normal state and 5
Insulation after 5 hours at 95% RH and 100 hours, Toa Denpa Co., Ltd., Super Megoheter Mod
It was measured using EL SM-5h.

(4) Results The above evaluation results are summarized and shown in Table 2. As is clear from the results in the table, the resist ink composition of the present invention has excellent exposure sensitivity as compared with conventional products,
The properties such as drying property and developing property are at the same level as conventional products. In addition, the resist film obtained by coating the resist ink composition of the present invention on a substrate is superior in hardness, electrical insulation resistance, water-soluble flux resistance and chemical resistance to conventional products, and the adhesion and solder heat resistance are at the same level as conventional products. Have.

[0048]

The resist ink composition of the present invention has excellent exposure sensitivity, can be easily photocured in a short exposure time, and can be easily developed with a weak alkaline aqueous solution such as sodium carbonate. it can. In addition, the resist film obtained by coating this on a substrate is superior in hardness, electric insulation resistance and chemical resistance to conventional products. Therefore, it can be used as an advanced highly reliable solder resist film. Moreover, since the resist coating comprising the resist ink composition of the present invention has a further improved water-soluble flux resistance, which was insufficient in the conventional similar products, it is a water-soluble flux-resistant resist that can withstand practically sufficient use. Can be preferably used as. The resist ink composition of the present invention can be used as an ink composition for various resists mainly used in the field of printed wiring boards such as chemical plating resists, in addition to the solder resists described above.

[Table 1]

[Table 2]

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location G03F 7/004 503 7/028 7/032 501 7/038 H05K 3/28 D 7511-4E // C08F 299 / 02 MRV (72) Inventor Masahiko Yoshimura 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Co., Ltd. Central Research Laboratory (72) Inventor Makoto Matsui 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Co., Ltd. Central Research Center

Claims (1)

[Claims] 1. An unsaturated compound obtained by reacting (A) 1,6-diglycidyloxynaphthalene with an unsaturated monobasic acid, (B) a reaction product of an epoxy compound and an unsaturated monobasic acid, It contains an actinic ray curable resin obtained by reacting with a saturated or unsaturated polybasic acid anhydride, (C) a photopolymerization initiator and (D) an epoxy compound having two or more epoxy groups in one molecule. And the mixing ratio of the unsaturated compound (A) and the actinic radiation curable resin (B) is 5 to 3 by weight.
0:95 to 70, and the mixture of the unsaturated compound (A) and the actinic radiation curable resin (B) as the photopolymerization initiator (C) 100.
2 to 30 parts by weight based on parts by weight, epoxy compound (D)
To 10 parts by weight of actinic ray curable resin (B).
A resist ink composition, characterized in that it comprises from about 50 parts by weight.