JP2988736B2 - One-part photosensitive thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the manufacture of printed wiring boards,
Used in metal precision processing, etc., relates to a novel photosensitive thermosetting resin composition particularly useful as a solder resist for printed wiring boards, and more specifically, selectively exposed to actinic rays through a patterned film, In the formation of solder resist by developing unexposed parts,
Excellent developability and resistance to developer in exposed areas,
One-part, long pot life, photosensitivity, adhesion, electrical insulation, contact resistance, solder heat resistance, solvent resistance, alkali resistance, acid resistance, and electrolytic gold, electroless gold, electroless copper, etc. The present invention relates to a photosensitive thermosetting resin composition for a solder resist having excellent plating resistance.

[0002]

2. Description of the Related Art Recently, printed wiring boards have made remarkable progress, and in particular, the integration of printed wiring boards has been accelerating due to the improvement of surface mounting technology. There is a demand for a method of forming a resist pattern having both of the above. For this reason, the demand for higher density of the solder resist ink is more severe, and the resolution used in the conventional method of forming a resist pattern on a printed wiring board by screen printing is low, and the method cannot be used. Therefore, in order to solve such problems, a dry film type photoresist using a high resolution photographic method and a photo development type liquid solder resist ink have been developed.

On the other hand, as a photo-developing type liquid solder resist ink, there is known a British patent application GB-2032939.
A publication discloses a photopolymerizable compound comprising a solid or semi-solid reaction product of an aromatic polyepoxide and an ethylenically unsaturated carboxylic acid, an inert inorganic filler, a photopolymerization initiator, and a volatile organic solvent. A coating composition is disclosed, and JP-A-60-208377 discloses a phenol novolak type epoxy acrylate, a cresol novolak type epoxy acrylate partially leaving an epoxy group, a photopolymerization initiator, and an amine curing agent. And a resin composition for a solder resist ink comprising an organic solvent.

Further, Japanese Patent Application Laid-Open No. Sho 61-243869
JP-A No. 2000-133873 discloses an active energy ray-curable composition obtained by reacting a reaction product of a novolak type epoxy compound with an unsaturated monocarboxylic acid and a polybasic acid anhydride using an aqueous alkali solution without using an organic solvent as a developer. Photocurable and thermosetting liquid resist ink compositions comprising a thermosetting component comprising a resin, a photopolymerization initiator, a diluent and an epoxy compound are disclosed.

[0005]

However, the dry film type photoresist has problems such as poor penetration into circuits, uneasiness such as blistering and poor adhesion of a coating film, and is expensive. Also, the disclosed photo-developing type liquid solder resist ink uses an organic solvent as a developer, so that environmental problems such as air pollution,
There is a problem that an expensive organic solvent must be used. Further, a liquid resist ink developable with an aqueous alkali solution described in JP-A-61-243869 and a commercially available liquid ink of an alkaline development type are prepared by reacting a novolak epoxy compound with an unsaturated monocarboxylic acid. It consists of two liquids, a main agent mainly composed of an active energy ray-curable resin obtained by reacting a product with a polybasic acid anhydride, and a curing agent mainly composed of an epoxy compound. In these two-part type photo-developing liquid resist inks, the carboxyl group present in the active energy ray-curable resin in the main agent and the epoxy group present in the epoxy compound in the curing agent react at room temperature. The pot life when these two liquids are mixed is as short as several hours to one day.

The current photo-developing liquid solder resist ink takes a long process of applying the solder resist ink → drying → exposure → development → post-curing. Then, the resist ink applied between the resist ink application and the development process is a dark reaction (thermal reaction)
As a result, problems such as poor development and poor development occur, and it is difficult to control the work process.

Further, since the resist ink is applied by a screen printing method and the pot life of the resist ink is short, a highly soluble fluorocarbon solvent such as trichloroethane is used for washing the screen plate. It has environmental problems such as air pollution and the problem that expensive organic solvents must be used. Also, coating methods such as an electrostatic coating method, a roll coater method, and a curtain coater method capable of continuous coating excellent in mass productivity and economic efficiency cannot be used because the pot life of the resist ink is short. When the thermosetting component composed of an epoxy compound is removed from the liquid resist ink composition disclosed in JP-A-61-243869, the pot life becomes longer, but the electrical properties of the resist ink, especially There is a problem that the performance is reduced. An object of the present invention is to provide a one-part liquid solder resist ink which can be developed with a dilute alkali solution and has excellent contact properties, gold plating resistance, workability and mass productivity without the above-mentioned disadvantages.

[0008]

Means for Solving the Problems The present inventors have intensively studied a method for improving the above-mentioned conventional problems, and as a result, have found that a photosensitive resin having a novolak-type epoxy resin as a skeleton reacted with a specific acid anhydride . By using prepolymer , photopolymerization initiator, diluent and thermosetting accelerator as essential components, it is suitable for resist pattern forming method that has both mass productivity and economic efficiency, and has good contact properties, gold plating resistance, and heat resistance. The present inventors have found that a one-pack type photo solder resist ink developable with an alkaline solution having excellent properties and the like can be obtained, and have completed the present invention. That is, the present invention relates to (A) an alicyclic dibasic anhydride obtained by reacting a reaction product of a novolak type epoxy compound with an unsaturated monobasic acid, a diolefin having 5 to 10 carbon atoms and maleic anhydride. Prepolymer obtained by reacting with a product, (B)
2-vinyl-4,6-diamino-S as a photopolymerization initiator, (C) a photopolymerizable vinyl monomer or oligomer as a diluent and / or an organic solvent, and (D) a thermosetting accelerator.
-Triazine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2,4-diamino-6
-Vinyl-S-triazine / isocyanuric acid adduct,
At least one of 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct
One is to provide a developable one-liquid photo solder resist ink composition with a dilute alkaline solution which comprises a.

[0009] Such a photosensitive thermosetting resin composition is
For example, on a printed wiring board on which a circuit is formed, screen printing, a roll coater, a curtain coater, or applied over the entire surface by spraying, or a dry film of the composition, or directly laminated on a printed wiring board, or A coating film can be formed by any method such as coating in a liquid state by a method and laminating a dry film thereon in a wet state or a dried state. Then, it is exposed to active light such as high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, chemical lamp and xenon lamp through direct irradiation of laser light or through a patterned photomask, and the unexposed part is developed with a developing solution. A pattern can be formed. Further, by post-curing with heat, a desired resist film is obtained.

That is, the photosensitive prepolymer (A) has 5 to 5 carbon atoms in addition to an —OH group formed by an esterification reaction between a novolak type epoxy compound and an unsaturated monobasic acid.
Diolefin having 10 and an alicyclic dibasic acid anhydride obtained by a Diels-Alder reaction are reacted to form a structure in which a number of free carboxyl groups are pendant on a side chain of the molecule, and developed with a dilute alkaline aqueous solution. The photosensitive prepolymer (A) obtained by adding these specific acid anhydrides is disclosed in JP-A-61-24.
Without containing a thermosetting component composed of an epoxy compound disclosed in Japanese Patent No. 3869, a one-part type liquid solder resist ink having a long pot life and excellent in electrical properties as a solder resist ink, particularly excellent in electrolytic corrosion resistance, can get.

In view of the above, the current screen printing method of the coating method makes it easy to control the working process and also supports the electrostatic coating method, the roll coater method, and the curtain coater method which are excellent in mass productivity. A one-part liquid solder resist ink is obtained. Further, in the one-part liquid solder resist ink composition of the present invention, since it does not contain epoxy, the carboxyl groups that are pendant in the photocurable resin are present in a free state, such as copper foil. Adhesion to metal increases, and a solder resist excellent in gold plating resistance can be obtained. Further, by using the specific thermosetting accelerator (D), post-curing by heat can be effectively performed, and a solder resist ink excellent in heat resistance and solvent resistance can be obtained.

The photosensitive prepolymer used in the present invention
(A) is an alicyclic ring obtained by a Diels-Alder reaction between an —OH group generated by an esterification reaction of a novolak epoxy compound and an unsaturated monobasic acid, and a diolefin having 5 to 10 carbon atoms and maleic anhydride. Obtained by reaction with group dibasic acid anhydride. In this case, the ratio between the novolak-type epoxy compound and the unsaturated monobasic acid is as follows:
0.8-1.1 mol, preferably 0.9-1.0 mol
Range of moles. If the amount of unsaturated monobasic acid is less than this range, the photocurability will be slow, and if the amount of unsaturated monobasic acid is outside this range, the storage stability of the reaction product will be poor. In particular, the photosensitive press obtained by reacting with the alicyclic dibasic acid anhydride
The storage stability of the polymer (A) deteriorates.

The ratio of the —OH group of the reaction product of the novolak type epoxy compound and the unsaturated monobasic acid to the alicyclic dibasic acid anhydride is as follows. The alicyclic dibasic acid anhydride is in an amount of 0.2 to 0.8 mol per -OH group of a reactant with an acid,
Preferably, it is in the range of 0.30 to 0.60 mol. The range of the acid value of the photosensitive prepolymer (A) thus obtained is 30 to 110 mgKOH / g, preferably 40 to 110 mgKOH / g.
90 mgKOH / g. If the acid value is less than 30, the solubility in an aqueous alkali solution is poor, and the developability is poor. Conversely, if it is higher than 110, the properties of the resist coating film deteriorate, which is not preferable. The novolak type epoxy compound used in the present invention refers to a resin obtained by reacting epichlorohydrin or methyl epichlorohydrin with a novolak resin obtained from a phenol compound and formaldehyde, and as a typical example, a phenol novolak type Epoxy resins, cresol novolak type epoxy resins, and the like can be given.

Typical examples of unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid cinnamate, acrylic acid dimer, monomethylmalate, monopropylmalate, monobutylmalate, and mono (2-ethylhexyl).
Typical examples of the alicyclic dibasic anhydride include 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and 3-methylhexahydrophthalic anhydride. , 4
-Methylhexahydrophthalic anhydride, hymic anhydride, methylhymic anhydride and the like.

Next, typical examples of the photopolymerization initiator (B) include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl methyl ketal, and alkyl ethers thereof; acetophenone 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone,
2,2-diethoxy-2-phenylacetophenone,
Acetophenones such as 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; methylanthraquinone, 2-ethylanthraquinone, 2- Anthraquinones such as tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone,
Thioxanthones such as 2-methylthioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and azo compounds.

These can be used alone or as a mixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate; Can be used in combination with a photo-initiating aid or the like. The amount used is 0.5 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the photocurable resin (A).

Further, as the diluent (C), an organic solvent and / or a photopolymerizable monomer can be used. Typical organic solvents include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol and isopropyl alcohol; esters such as ethyl acetate and butyl acetate; ethers such as 1,4-dioxane and tetrahydrofuran. Ketones such as methyl ethyl ketone and methyl isobutyl ketone; glycol derivatives such as cellosolve and butyl cellosolve; alicyclic hydrocarbons such as cyclohexanone and cyclohexanol; and petroleum solvents such as petroleum ether and petroleum naphtha.

On the other hand, typical photopolymerizable vinyl monomers include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and isobornyl ( Esters of (meth) acrylic acid such as (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and phenoxydiethylene glycol (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol triester Hydroxyalkyl (meth) acrylates such as (meth) acrylate;

Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate A) alkylene polyol poly (meth) acrylates such as acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; Diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate polyethylene glycol 200 di (meth)
Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, ethoxylated hydrogenated bisphenol A Di (meth) acrylate, propoxylated hydrogenated bisphenol A di (meth) acrylate,

Polyoxyalkylene glycol poly (meth) acrylates such as ethoxylated dicyclopentanierdi (meth) acrylate and propoxylated dicyclopentanierdi (meth) acrylate; neopentyl glycol ester hydroxyhydroxyvalate di (meth) acrylate ) Ester-type poly (meth) acrylates such as acrylates; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate; N, N-dimethylaminoethyl (meth) acrylate; , N-dimethylaminopropyl (meth)
Aminoalkyl (meth) acrylates such as acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl Acrylamide, N, N
-(Meth) acrylamides such as dimethyl (meth) acrylamide and (meth) acryloylmorpholine; vinylpyrrolidone;

The diluent (C) may be used alone or
Used as a mixture of more than one species. The amount used is
20 per 100 parts by weight of the photosensitive prepolymer (A)
A suitable amount is from 200 to 200 parts by weight, preferably from 30 to 150 parts by weight. Here, the purpose of using the organic solvent and the photopolymerizable vinyl monomer is as follows.
The polymer (A) is dissolved and applied so as to have a viscosity suitable for various coating methods such as an electrostatic coating method and a roll coater method, and then dried to form a photopolymerizable film. Further, the photopolymerizable vinyl monomer imparts photopolymerizability, and the water-soluble photopolymerizable vinyl monomer also serves to assist solubility in an aqueous alkaline solution. However, if the photopolymerizable vinyl monomer is used in a large amount, it is impossible to form a photopolymerizable film having no tack after drying. The resolution of the pattern is reduced.
In addition, since chemical resistance and electrical characteristics are also reduced,
The use amount thereof is preferably not more than 50 parts by weight of the photosensitive prepolymer (A).

Further, various additives such as fillers such as talc, barium sulfate, silica and clay; thixotropic agents such as aerosil; phthalocyanine blue, phthalocyanine green, and oxidizing agent are added to the liquid solder resist ink composition of the present invention. Coloring agents such as titanium; silicone and fluorine-based leveling agents and defoaming agents; and polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be added for the purpose of enhancing various properties of the solder resist ink.

[0023] Thermal curing accelerator (D) is used in alone. The amount used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the photocurable resin (A).
The ratio by weight is appropriate. Typical examples of the thermosetting accelerator include 2-vinyl-4,6-diamino-S-triazine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, and 2,4-diamino-6-vinyl-S-triazine. Isocyanuric acid adduct, 2,4
- a diamino 6-methacryloyloxyethyl over S- triazine isocyanuric acid adduct. Here, the purpose of using the thermosetting accelerator is to promote post-curing by heat, and as a result, it is possible to improve solder heat resistance, solvent resistance, chemical resistance, and the like.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. All parts and percentages are by weight unless otherwise specified. (Example 1) Obtained by reacting 1.0 mol of acrylic acid per one epoxy group of a cresol novolak type epoxy resin “Epiclon N-673” (epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 215. 3-
0.30 mol of methyltetrahydrophthalic anhydride was reacted by a conventional method using cellosolve acetate as a solvent to obtain a photosensitive prepolymer (A) having an acid value of 49.9 mgKOH / g.
-1) was obtained. Cellosolve acetate is the photosensitive pre-press
An amount of 40 parts by weight based on 100 parts by weight of the polymer (A-1) was used. Photosensitive prepolymer thus obtained
- (A-1), a photopolymerization initiator, an organic solvent, and an additive were blended as described below, and kneaded using a three-roll mill to prepare a resist ink. Next, the prepared resist ink is applied by a screen printing method so as to have a thickness of 15 to 25 μm on a degreased and washed copper-clad laminate or a printed wiring board having a pattern formed on a comb-shaped electrode plate.
After drying for 20 minutes, the negative film was brought into close contact with the coated surface and exposed using a metal halide lamp exposure device manufactured by Oak Manufacturing Co., Ltd., and then developed at 30 ° C. for 60 seconds using a 1% by weight aqueous solution of sodium hydrogencarbonate. Heat treatment was performed at 150 ° C. for 30 minutes using a hot-air drying furnace to prepare a specimen.

Formulation The above photosensitive prepolymer (A-1) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts 2-vinyl-4,6-diamino-S-triazine 5 parts

Example 2 A reaction product obtained by reacting 0.95 mol of acrylic acid per epoxy group of “Epiclon N-673” was
0.40 mol of 4-methylhexahydrophthalic anhydride is reacted by a conventional method using cellosolve acetate as a solvent,
A photosensitive prepolymer (A-2) having an acid value of 64.0 mgKOH / g was obtained. Cellosolve acetate is the photosensitive
An amount of 40 parts by weight based on 100 parts by weight of the prepolymer (A-2) was used. Next, a specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation Photosensitive prepolymer (A-2) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts 2-vinyl-4,6-diamino-S-triazine 5 parts

Example 3 1.0 mol of acrylic acid was reacted per epoxy group of a phenol novolak type epoxy resin "Epiclon N-740" (epoxy resin manufactured by Dainippon Ink and Chemicals, Inc.) having an epoxy equivalent of 185. The resulting reaction product was reacted with 0.5 mol of hymic anhydride by a conventional method using butyl cellosolve as a solvent, and the acid value was 82.5 mgKOH / g.
A photosensitive prepolymer (A-3) was obtained. Solosolve acetate is 10% of the photosensitive prepolymer (A-3).
An amount of 30 parts by weight with respect to 0 parts by weight was used. Next, a specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation The above photosensitive prepolymer (A-3) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts 2-vinyl-4,6-diamino-S-triazine 5 parts

Example 4 A reaction product obtained by reacting 1.0 mol of acrylic acid per epoxy group of “Epiclon N-740” was added with 3
-0.6 mol of methyltetrahydrophthalic anhydride is reacted by a conventional method using petroleum naphtha as a solvent, and the acid value is 94.0.
A photosensitive prepolymer (A-4) of mgKOH / g was obtained. Petroleum naphtha was used in an amount of 30 parts by weight based on 100 parts by weight of the photosensitive prepolymer (A-4). Next, a specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation The above photosensitive prepolymer (A-4) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts 2-vinyl-4,6-diamino-S-triazine 5 parts

Example 5 A reaction product obtained by reacting 1.0 mol of acrylic acid per epoxy group of “Epiclone N-673” was added with 4
-0.7 mol of methyltetrahydrophthalic anhydride is reacted by a conventional method using petroleum naphtha as a solvent, and the acid value is 97.2.
A photosensitive prepolymer (A-5) of mgKOH / g was obtained. Petroleum naphtha was used in an amount of 40 parts by weight based on 100 parts by weight of the photosensitive prepolymer (A-5). Specimens were prepared in the same manner as in Example 1 except that they were blended as follows. Formulation The above photosensitive prepolymer (A-5) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts 2-vinyl-4,6-diamino-S-triazine 5 parts

Example 6 A specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation The above photosensitive prepolymer (A-1) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts 2,4-Diamino-6-vinyl-S-triazine isocyanuric acid adduct 5 parts

Example 7 A specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation The above photosensitive prepolymer (A-1) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct 5 parts

(Comparative Example 1) A test piece was prepared in the same manner as in Example 1 except that the following compounding was carried out. Formulation The above photosensitive prepolymer (A-1) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 copies

Comparative Example 2 A reaction product obtained by reacting 0.95 mol of acrylic acid per epoxy group of “Epiclone N-673”
0.4 mol of succinic anhydride was reacted by a conventional method using cellosolve acetate as a solvent, and the acid value was 69.3 mg KOH.
/ G of the photosensitive prepolymer (A-6). Petroleum naphtha was used in an amount of 40 parts by weight based on 100 parts by weight of the photosensitive prepolymer (A-6). Next, a specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation The above photosensitive prepolymer (A-6) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 copies

Comparative Example 3 A reaction product obtained by reacting 0.95 mol of acrylic acid per epoxy group of “Epiclone N-673” was
0.4 mol of tetrahydrophthalic anhydride is reacted by a conventional method using cellosolve acetate as a solvent, and the acid value is 65.
A photosensitive prepolymer (A-7) having a concentration of 3 mgKOH / g was obtained. Petroleum naphtha is the photosensitive prepolymer (A-7)
Was used in an amount of 40 parts by weight with respect to 100 parts by weight.
Next, a specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation The above photosensitive prepolymer (A-7) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 copies

Comparative Example 4 0.6 mol of hexahydrophthalic anhydride and petroleum naphtha were added to a reaction product obtained by reacting 1.0 mol of acrylic acid per epoxy group of “Epiclone N-740”. The reaction was carried out by a conventional method as a solvent, and the acid value was 88.6 mgKOH.
/ G of a photosensitive prepolymer (A-8). Petroleum naphtha was used in an amount of 30 parts by weight based on 100 parts by weight of the photosensitive prepolymer (A-8). Next, a specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation The above photosensitive prepolymer (A-8) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 copies

(Comparative Example 5) A specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation Photosensitive prepolymer of Example 1-1 (A-1) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts DICY 5 parts

(Comparative Example 6) A specimen was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation Photosensitive prepolymer of Example 1-1 (A-1) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts 2MA-OK (2,4-diamino-6 ｛2'-methylimidazaolyl (1) '｝ ethyl-S-triazine / isocyanuric acid adduct) 5 parts

(Comparative Example 7) A test piece was prepared in the same manner as in Example 1 except that the components were blended as follows. Formulation Photosensitive prepolymer of Comparative Example 3 (A-7) 100 parts Dipentaerythritol hexaacrylate 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinol 1-propanone 5 parts Barium sulfate 25 parts Carbitol acetate 50 parts DICY 3 parts Cresol novolak type epoxy resin 30 parts

[0039]

[Table 1]

The test items, methods and criteria are as follows. (1) Adhesion test According to the test method of JIS D0202, a cross cut was made in the shape of a substrate, and then a peeling test was performed with a cellophane tape. …: No peeling was observed at 100 measurement points △: Peeling was observed at 1 to 50 points of 100 measurement points ×: Peeling was observed at 51 to 100 points of 100 measurement points Is recognized

(2) Pencil hardness test Measured under a load of 1 kg according to the test method of JIS D0202. (3) Solder heat resistance According to JIS C 6481, the state of the coating film was evaluated by immersion in a 260 ° C. solder bath for 15 seconds. When no abnormality was observed in the coating film, immersion was repeated for 15 seconds, and the maximum number of times that no abnormality was observed in the coating film was expressed.

(4) Electroless plating resistance A specimen was prepared using a copper-clad laminate under the above conditions, and then degreased.
Pretreatment such as activation was performed, immersed in an electroless nickel plating solution at 90 ° C. for 20 minutes, washed with water and diluted hydrochloric acid, and then immersed in an electroless gold plating solution at 90 ° C. for 20 minutes. The resist ink coating film after the gold plating treatment was subjected to a peeling test using a cellophane tape, and the degree of peeling of the coating film was visually determined. …: No peeling was observed. Δ: slight peeling is observed. ×: considerable peeling is observed.

(5) Pot Life The resist inks prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were put in a container, sealed, and stored in a thermostat at 25 ° C. for a certain period of time. Thereafter, each resist ink is applied to the entire surface of the copper-clad laminate by screen printing so as to have a thickness of 15 to 25 μm, and dried at 80 ° C. for 20 minutes. A test piece was prepared by exposing using a metal halide lamp exposing apparatus manufactured by Co., Ltd., and developability with a 1% by weight aqueous solution of sodium hydrogen carbonate was evaluated. The measured value of the pot life was represented by the maximum storage time in which the resist ink could be developed.

(6) Insulation Resistance A specimen was prepared using a printed wiring board having a pattern formed in a 0.318 mm pitch comb-shaped electrode shape, and was heated at 60 ° C. and 90 ° C.
% RH and 24 V, and the insulation resistance value after 400 hours was measured using SM-10E manufactured by Toa Denpa Co. (500 V applied). (7) Electrodeability Using a specimen treated under the same conditions as the measurement conditions of the insulation resistance, the presence or absence of migration was confirmed. ○: No migration occurred ×: Migration occurred

[0045]

The resist ink composition of the present invention is useful as a one-part liquid solder resist ink which can be developed with a dilute alkaline solution having excellent contact properties, gold plating resistance, workability and mass productivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H05K 3/28 H05K 3/28 D (72) Inventor Iwasa Yamadai 251 Suwa-cho, Hachioji-shi, Tokyo Inside Asahi Chemical Laboratory Co., Ltd. 56) References JP-A-2-173747 (JP, A) JP-A-2-294371 (JP, A) JP-A-2-43551 (JP, A) JP-A-4-165357 (JP, A) JP Hei 3-253093 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/027 C09D 11/00 C09D 11/10 G03F 7/004 G03F 7/028 H05K 3/28

Claims (3)

(57) [Claims] 1. An alicyclic dibasic anhydride obtained by reacting (A) a reaction product of a novolak type epoxy compound with an unsaturated monobasic acid, a diolefin having 5 to 10 carbon atoms and maleic anhydride. Photoreceptor obtained by reacting
Limmer , (B) a photopolymerization initiator, (C) a photopolymerizable vinyl monomer or oligomer as a diluent and / or an organic solvent, and (D) 2-vinyl-4,6 as a thermosetting accelerator.
-Diamino-S-triazine, 2,4-diamino-6-
Methacryloyloxyethyl-S-triazine, 2,4
- diamino 6-vinyl-S- triazine isocyanuric acid adduct, 2,4-diamino 6-methacryloyloxyethyl over S- triazine isocyanuric acid adduct
A one-pack type photo solder resist ink composition developable with a dilute alkali solution, comprising at least one . 2. A reaction product of a secondary hydroxyl group of an esterified product of the photosensitive prepolymer produced by an esterification reaction of a novolak type epoxy compound with an unsaturated monocarboxylic acid and a saturated or unsaturated polybasic acid anhydride. The one-pack type photo solder resist ink composition according to claim 1, which is: 3. A one-part photo solder resist ink composition according to claim 1 the amount of diluent is the photosensitive prepolymer <br/> over 20 to 300 parts by weight per 100 parts by weight.