JPH0284413A - Photosensitive resin composition for chemical plating - Google Patents

Abstract

PURPOSE:To obtain the title composition readily photocurable, to be used for forming protective films by incorporating a silane coupling agent as an adherability improver into a composition comprising a specific ethylenic unsaturated compound, thermoplastic polymer, polymerization initiator and thermal polymerization inhibitor. CONSTITUTION:The objective composition comprising (A) an ethylenic unsaturated compound liquid or solid at normal temperature, containing at least two ethylenic unsaturated bonds and capable of forming a polymer by addition polymerization using a photopolymerization initiator [e.g., (meth)acrylic ester], (B) a thermoplastic polymer (e.g., polyvinyl butyral), (C) a photopolymerization initiator capable of generating free radicals by active ray irradiation (e.g., 2-ethyl anthraquinone), (D) a thermal polymerization inhibitor (e.g., p- methoxyphenol), and (E) a silane coupling agent as an adherability improver.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive resin composition that is easily photocured and used to form a protective film for chemical plating and soldering. More specifically, the present invention relates to a photosensitive resin composition that can be used as a protective film for chemical plating and soldering, and has excellent adhesion to copper foil.

[Conventional technology]

Solder masks protect the conductors from corrosion, restricting the soldering area when performing soldering. It is applied for purposes such as maintaining electrical insulation between conductors.

Traditionally, thermosetting resins such as epoxy resins were screen printed, but as wiring patterns become denser, screen printing methods are no longer able to provide satisfactory accuracy, and fine pattern printing is becoming increasingly difficult. For this purpose, photoengraving is becoming necessary.

For these reasons, photosensitive resin compositions that can be subjected to photoengraving are disclosed in Japanese Patent Publication No. 61-243869.

This was proposed in Japanese Patent Publication No. 62-7774. Also,
The method described in JP-A No. 53-56018 regarding a flame retardant for forming a solder mask, and the method described in JP-A-59-23723 and JP-A-60-1885 regarding compositions with improved thermal shock resistance. Proposals have been made for methods described in gazettes, etc.

Although the proposed materials are excellent in heat resistance or thermal shock resistance, which is the purpose of the proposal.

When used as a resist for chemical plating described below, the following problems occur.

That is, instead of the conventional subtractive method for forming wiring patterns, copper wiring can be formed only in necessary areas by chemical plating, so that etching of copper foil and disposal of its waste liquid can be omitted. Through-holes, especially small diameter (0.4+ua or less), can reduce costs.
Chemical plating baths for additive methods, which have many advantages such as being able to improve the reliability of through-holes in Although operated at high temperatures of 0.degree. C., the above composition cannot be used under such harsh conditions.

[Problem to be solved by the invention]

The present inventors have conducted research and development on photosensitive resin compositions that can be used in additive methods, particularly in part-additive methods in which only through holes are formed by chemical plating. It does not change after chemical plating or soldering, but due to poor adhesion between the photosensitive resin layer and the copper foil formed as a wiring pattern on the base material, the plating solution does not change the copper during the chemical plating process. A phenomenon occurred in which the resin penetrated into the interface between the foil and the resin layer, and the resin layer rose from the base material. Moreover, due to this phenomenon, cracks and peeling occurred in the resin layer during subsequent soldering processing.

The present invention was made to solve the above-mentioned problems, and can be used as a protective film for chemical plating and soldering, and has excellent adhesion to copper foil, preventing penetration of plating solution and preventing resin layer An object of the present invention is to provide a photosensitive resin composition that does not cause a phenomenon such as floating.

[Means to solve the problem]

The present invention is the following photosensitive resin composition for chemical plating.

(1) (a) Ethylenically unsaturated, containing at least two or more ethylenically unsaturated bonds, capable of forming a polymer in addition polymerization initiated by a photopolymerization initiator, and being liquid or solid at room temperature compound, (b) thermoplastic polymer compound.

(c) A photopolymerization initiator that generates free radicals upon irradiation with actinic light.

(d) A photosensitive resin composition for chemical plating, which is a composition containing a thermal polymerization inhibitor, and (e) a silane coupling agent is added as an adhesion improver.

(2) (a) Contains at least two ethylenically unsaturated bonds and can form a polymer in addition polymerization initiated by a photopolymerization initiator. Ethylenically unsaturated compounds that are liquid or solid at room temperature; (b) thermoplastic polymer compounds;

(c) a photopolymerization initiator that generates free radicals when irradiated with actinic light; (d) a composition containing a thermal polymerization inhibitor; and (e) a composition containing a phthalocyanine compound as an adhesion improver. Photosensitive resin composition for plating.

In other words, the present invention is directed to a compound containing at least two or more ethylenically unsaturated bonds, which is liquid or solid at room temperature and capable of forming a polymer through addition polymerization initiated by a photopolymerization initiator, and a thermoplastic compound. By adding a silane coupling agent or a phthalocyanine compound as an adhesion improver to a photosensitive resin composition consisting of a polymer compound, a photopolymerization initiator that generates free radicals upon irradiation with actinic light, and a thermal polymerization inhibitor. This greatly improves adhesion to copper foil, solving problems such as penetration of plating solution and lifting of the resin layer during chemical plating.

The silane coupling agent used in the present invention is an organosilicon monomer having at least two different reactive groups in its molecule. One reactive group is a methoxy group that forms a chemical bond with an inorganic substance.

Examples include ethoxy group and cellosolve group. Other reactive groups include vinyl groups, acrylic groups, methacrylic groups, epoxy groups, amino groups, mercapto groups, etc. that chemically bond with the resin component. An example of such a silane coupling agent is vinyl tris (β-
methoxy) silane.

Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane Examples include methoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane. Among these, acrylic-based, vinyl-based, and epoxy-based silane coupling agents are particularly desirable, and examples of such silane coupling agents include C-methacryloxypropyltrimethoxysilane,
Examples include γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyljethoxysilane. The amount of the silane coupling agent added is 0.05 to 20% based on the weight of the photosensitive resin composition.
% by weight, preferably 0.1-5% by weight.

The phthalocyanine compound used in the present invention is represented by the following general formula and is commonly used as a blue or green organic pigment or dye.

(X=H, CQ, -C(c)I3)3, OPh, C0O
H.

The amount of the phthalocyanine compound added is 0.05 to 20% by weight, preferably 0.05 to 20% by weight, based on the weight of the photosensitive resin composition.
It is 1 to 10% by weight. Since the phthalocyanine compound is an organic pigment or dye, it is not necessarily necessary to add other pigments or dyes to color the composition.

The ethylenically unsaturated compound used in the present invention contains at least two or more ethylenically unsaturated groups, and forms a polymer with a photopolymerization initiator. A compound that is liquid or solid at room temperature and atmospheric pressure. Examples of such ethylenically unsaturated compounds include (meth)acrylic acid esters, allyl compounds, vinyl ether compounds, vinyl ester compounds, and cinnamic acid ester compounds. As the (meth)acrylic acid ester, epoxy (meth)acrylate obtained from the reaction of a bifunctional or more functional epoxy resin and a carboxylic acid having an ethylenically unsaturated bond;
Examples include urethane (meth)acrylate obtained by reacting polyvalent aromatic isocyanate or polyvalent aliphatic isocyanate with (meth)acrylic acid monoester of dihydric alcohol, and (meth)acrylate of polyhydric alcohol. Allyl compounds include phthalic acid, adipic acid,
Examples include diallyl esters such as malonic acid. Examples of the vinyl ether compound include vinyl ether compounds of polyhydric alcohols. Examples of the vinyl ester compound include divinyl succinate, divinyl phthalate, divinyl adipate, etc., and examples of the cinnamic acid ester include polyvinyl cinnamate.

The thermoplastic polymer compound used in the present invention is:

Adjust the viscosity, film strength, and film smoothness of the resin composition,
It is used to improve the properties of the resin composition and is compatible with the above-mentioned ethylenically unsaturated compound. Such substances include vinyl polymer compounds such as polyvinyl butyral, polyvinyl chloride, and polyvinyl acetate, as well as acrylic acid, methacrylic acid, methyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl acrylate, (meth) Examples include vinyl polymer compounds such as vinyl heptad polymers and copolymers, typified by acrylamide.

Photopolymerization initiators that generate free radicals upon irradiation with actinic light used in the present invention include 2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone,
Quinones such as 3-diphenylanthraquinone, d-ketal vinyl alcohols such as benzoin, bivaloin, and acyloin ether, ethers, d, d'-jethoxyacetophenone, benzophenone, 4,4-bisalkylaminobenzophenone, etc. Ketones, 2
, 4,5-triarylimidazolyl dimer and the like. These can be used alone or in combination.

The thermal polymerization inhibitor is used to prevent thermal polymerization during storage of the resin composition and during the protective film formation process. Examples of such substances include domethoxyphenol, hydroquinone, pyrogallol, zenathiazine, and β-naphthol.

The photosensitive resin composition of the present invention can be applied directly onto a substrate on which a wiring pattern has been formed to form a dried hindlimb composition film, or alternatively can be applied onto a suitable film support such as polyethylene terephthalate and dried. After forming a film-like material in advance, it is pressed onto a substrate.

Since the printed circuit board has many holes such as component insertion holes, mounting holes, and through holes for conduction between different surfaces above the face plate, it is important to prevent liquid resin from entering these holes. In order to prevent this, it is preferable to use a method of press-bonding a film-like material formed on a film support.

The formation of a protective film pattern (electronic light, development) after coating the composition on the substrate can be performed by information. That is, exposure is performed through a negative mask using a light source such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a metal halide lamp.

After exposure, heat treatment is performed at 50 to 100° C. for 10 to 30 minutes, the support film is peeled off, and then development is performed using a solvent such as 1,1,1-trichloroethane.

The image-like protective film obtained by this method serves as a corrosion-resistant film for ordinary etching, plating, etc., but even better properties can be obtained by heat treatment at 80-200°C and irradiation with actinic light after development. It becomes a protective film with This treatment is usually carried out after irradiation with active light, followed by heat treatment for 30 to 30 minutes.
Preferably, this is carried out for 60 minutes.

The film obtained by heat treatment after development and irradiation with actinic light sufficiently resists organic solvents such as tricrene, methyl ethyl ketone, isopropyl alcohol, and toluene, and also resists acidic or alkaline aqueous solutions. Furthermore, it has excellent heat resistance, with cold and heat resistance f71! Because it has excellent properties, it is suitable as a permanent protective film for solder masks and other products that require long-term reliability.

In addition, because the resin composition and copper foil are in very strong adhesion, even if chemical plating is performed for a long time, there will be no penetration of the plating solution or lifting from the base material as described above. .

〔Example〕

Next, examples of the present invention will be described. The examples shown here are illustrative of embodiments, and the invention is not limited thereto. In each example, 1 part and 1% are based on weight.

Example 1 (1) Synthesis of epoxy acrylate 430 g of novolac type epoxy resin (EOCN-1021 manufactured by Nippon Kayaku Co., Ltd., trade name, epoxy equivalent weight 215), 130 g (1.8 equivalents) of acrylic acid, Triclene 24
0g was placed in an IQ flask, and 0.4g (approximately 0.1%) of p-methoxyphenol and 1.8g (0.5%) of benzyldimethylamine were added as polymerization inhibitors.
The reaction was carried out at ℃ for 5 hours. The end point of the reaction was determined by measuring the acid value using a conventional method, and was determined to be the point at which the value became 1 or less.

(2) Synthesis of epoxy acrylate Epicote 828 (manufactured by Yuka Shell Co., Ltd., trademark, epoxy equivalent: 190) 570 g (3 equivalents) and acrylic acid 201
g (2.8 mol) into an IQ flask, and 0.77 g (0.1%) of ρ-methoxyphenol as a polymerization inhibitor.
, 3.9 g (0.5%) of benzyldimethylamine were added thereto, and the mixture was reacted at 90° C. for 6 hours. Thereafter, the acid value was measured by a conventional method, and the end point of the reaction was determined when the value became 1 or less.

(3) Preparation of photosensitive resin composition solution 40 parts of the epoxy acrylate solution obtained in (1) above (
Resin content: 24 parts) Epoxy acrylate obtained in (2) above: 30 parts Methyl ethyl ketone: 46 parts Photosensitive resin composition solution with the above composition! ! ! Manufactured.

(4) Creation of photosensitive resin film This resin solution was applied onto a polyethylene terephthalate film with a thickness of 25 microns, dried at room temperature for 20 minutes, at 70°C for 10 minutes, and at 100°C for 5 minutes. A film-like product having a composition layer thickness of about 70 microns was obtained.

(5) Formation of protective film Through holes and component holes were formed in a glass epoxy copper-clad laminate with a base material thickness of 6 x 1.6 m+w and a copper foil thickness of 18 microns. Next, after performing a catalyst treatment for chemical plating, a wiring pattern was formed by etching.

The film-like material obtained in (4) was laminated onto the substrate using a laminator. After lamination, exposure paper was applied through a negative mask, and after heating at 80°C for 10 minutes, spray development was performed using 1,1,1-trichloroethane. (20
℃, 80 seconds) fI74. After imaging, dry at 80°C for 5 minutes and heat at 2.5J/c using a high-pressure mercury lamp (8011/ad).
d light was irradiated. Thereafter, heat treatment was performed at 150° C. for 30 minutes to form a protective film.

(6) Chemical copper plating Next, chemical steel plating bath (P) 112.5 (20°C), 6
The substrate was immersed for 16 hours at 0° C., and copper plating approximately 25 microns thick was applied to the through holes and component holes. After chemical plating treatment, rinse thoroughly with water, and then heat at 80℃ for 10 minutes.
After drying for minutes, heat treatment was performed at 130° C. for 60 minutes.

During this series of chemical copper plating treatments, no deterioration, peeling, blistering, etc. of the protective film occurred, and sufficient resistance was exhibited.

Furthermore, neither penetration of the plating solution onto the copper wiring nor lifting of the protective film from the base material was observed.

Furthermore, as a soldering heat resistance test, the protective film was immersed in a solder bath at 255 to 265° C. for 10 seconds, but the protective film was stable and no cracking or peeling was observed, indicating that it could be used satisfactorily as a solder mask.

Example 2 (1) Synthesis of urethane acrylate 444 g (4 equivalents) of isophorone diisocyanate, 300 g of toluene, 0.3 di-n-butyltin dilaurate
of 1,6-
236 g (4 equivalents) of hexanediol was added dropwise over about 2 hours, and the mixture was reacted at 80° C. for 5 hours. Then, the temperature was lowered to 60°C, 8 g of methanol was added as a stopper, and 1
After stirring for hours, a urethane acrylate with a resin content of 70% was obtained.

(2) Synthesis of bisphenol-type epoxy acrylate ER332 (manufactured by Dow Chemical Company, trademark, epoxy equivalent: 3)
30) 173 g (1 equivalent) and DER542 (manufactured by Dow Chemical Company, trademark, bromine content 46%, epoxy equivalent weight 330)
660g (2 bins) and 201g of acrylic acid (2,8
mol) into an IQ flask, add 1. Og (0.1%), benzylmethylamine5. Ig
(0.5%) was added.

The reaction was carried out at 90°C for 6 hours. Others are (2) of Example 1.
) Epoxy acrylate was synthesized by the same procedure as described above.

(3) Preparation of photosensitive resin composition solution Urethane acrylate obtained in the above (1) 40 parts (solid content 28 parts) Epoxy acrylate obtained in the above (2)
13 part benzophenone
7 parts N,N-dimethylaminobenzophenone
1 part hydroquinone
0.1 part phthalocyanine green
5 parts γ-methacryloxypropyltrimethoxysilane 3 parts Methyl ethyl ketone
40 parts of a photosensitive resin composition solution having the above composition was prepared.

A protective film was formed on the substrate using this resin solution in the same manner as in Example 1. Next, chemical copper plating was performed in the same manner as in Example 1. After this, sufficient water washing and drying were performed. During this series of chemical copper plating treatments, no deterioration, lifting, peeling, or penetration of the plating solution was observed in the protective film, indicating sufficient protection and adhesion to copper.

Example 3 Preparation of photosensitive resin composition solution A photosensitive resin composition solution was prepared using the compounds shown below.

Polyvinyl cinnamate (M, W, =5000)
50 parts pentaerythritol triacrylate 10 parts 2-ethylanthraquinone
5 parts p-methoxyphenol
0.1 part γ-glycidoxypropylmethyljethoxysilane 3 parts Methyl ethyl ketone 40 parts The same operation as in Example 1 was performed using the above composition to form a protective film on the substrate. When this substrate was plated in the same manner as in Example 1, no deterioration, lifting, peeling, or penetration of the plating solution of the protective film was observed. After this, soldering was performed, but no change was observed in the protective film.

Example 4 Preparation of photosensitive resin composition solution 60 parts of the epoxy acrylate (1) of Example 1 (
Solid content 36 parts) Trimethylolpropane triacrylate 14 parts Methacrylic acid copolymer used in Example 2 20 parts 2-ethylanthraquinone
5 parts r methoxyphenol
0.05 parts γ-methacryloxypropyltrimethoxysilane 5 parts Methyl ethyl ketone
28 parts Example 1 with the above composition
A protective film was formed on the substrate by performing the same operation as above. When this substrate was subjected to chemical plating in the same manner as in Example 1, no deterioration, lifting, peeling, or penetration of the plating solution of the protective film was observed.

Example 5 Preparation of photosensitive resin composition solution 35 parts of urethane acrylate obtained in (1) of Example 2 (
Resin content 25 parts) Pentaerythritol triacrylate 20 parts Methacrylic acid copolymer used in Example 3 40 parts Irgacure 9075 parts Hydroquinone 0
．． Part 1 Victoria Blue
0.5 parts γ-methacryloxypropyltrimethoxysilane 3 parts toluene
50 parts A photosensitive resin composition solution was prepared according to the above composition, and a protective film was formed on a substrate in the same manner as in Example 1.

Next, chemical copper plating treatment was performed in the same manner as in Example 1, and no deterioration, lifting, peeling, or penetration of the plating solution of the protective film was observed. Subsequently, soldering was performed, but no change was observed.

Comparative Example 1 Preparation of photosensitive resin composition solution Epoxy acrylate obtained in Example 1 (1) 40 parts (resin content 24 parts) Epoxy acrylate obtained in Example 1 (2) 30 parts Used in Example 1 Polyvinyl butyral 35 parts Benzophenone
7 parts N,N-dimethylaminobenzophenone 1 part hydroquinone
0.1 part methylene blue
5 parts Methyl ethyl ketone 46 parts A photosensitive resin composition solution having the above composition was prepared, and a protective film was formed on the substrate in the same manner as in Example 1.6 Next, chemical copper plating was performed in the same manner as in Example 1. .

After this, sufficient water washing and drying were performed.

After chemical plating, no deterioration of the protective film itself was observed, but penetration of the plating solution onto the copper wiring and lifting of the protective film around the lands were observed. When the substrate was floated in a solder bath (260° C.) for 10 seconds, the protective film peeled off at the areas penetrated by the plating solution and at the floating areas.

Comparative Example 2 Photosensitive resin composition solution made by vR Epoxy acrylate obtained in Example 1 (1) 40 parts (resin content 24 parts) Polyvinyl butyral used in Example 1 35 parts N,N-dimethylaminobenzophenone 1 part hydroquinone
0.1 part methylene blue
5 parts γ-methacryloxypropyltrimethoxysilane 0.01 parts Methyl ethyl ketone 46 parts A photosensitive resin composition solution having the above composition was prepared, and a protective film was formed on a substrate in the same manner as in Example 1.

Next, chemical copper plating was performed in the same manner as in Example 1. After this, sufficient water washing and drying were performed.

After chemical plating, no deterioration of the protective film itself was observed, but penetration of the plating solution onto the copper wiring and lifting of the protective film around the lands were observed. When the substrate was floated in a solder bath (260° C.) for 10 seconds, the protective film peeled off at the areas penetrated by the plating solution and at the floating areas.

Comparative Example 3 Preparation of photosensitive resin composition solution Urethane acrylate of Example 2 (1) 40 parts (solid content 28 parts) Epoxy acrylate of Example 2 (2) 13 parts Methacrylic acid used in Example 2 Polymer 40 parts Irgacure 9077 parts Hydroquinone
0.1 part phthalocyanine green
5 parts methyl ethyl ketone
40 parts A photosensitive resin composition solution having the above composition was prepared, and a protective film was formed on a substrate in the same manner as in Example 1.

Next, chemical copper plating was performed in the same manner as in Example 1. After this, sufficient water washing and drying were performed.

After chemical plating, no deterioration of the protective film itself was observed, but penetration of the plating solution onto the copper wiring and lifting of the protective film around the lands were observed. When the substrate was floated in a solder bath (260°C) for 10 seconds, the parts penetrated by the plating solution and
The protective film peeled off at the floating parts.

From these results, when the silane coupling agent is not added, or when the amount added is outside the range of the present invention,
It can be seen that the desired characteristics cannot be obtained.

Example 6 (1) Preparation of photosensitive resin composition solution A photosensitive resin composition solution was prepared using the compounds shown below.

Polyvinyl cinnamate (M, V, =5000)
50 parts pentaerythritol triacrylate 10 parts Copolymer of methyl methacrylate and methacrylic acid at a polymerization ratio (90/10) (molecular weight approximately 230,000)
40 parts 2-ethylanthraquinone
5 parts P-methoxyphenol
o, i Phthalocyanine compound shown in the lower formula 5 parts methyl ethyl ketone
40 parts (2) Preparation of a photosensitive resin film This resin solution was applied onto a polyethylene terephthalate film with a thickness of 25 microns and kept at room temperature for 20 minutes.

It was dried at 70° C. for 10 minutes and at 100° C. for 5 minutes to obtain a film-like product with a photosensitive resin composition layer having a thickness of about 70 microns.

(3) Formation of protective film A glass epoxy copper clad laminate with a base material thickness of 1.6 mm and a copper foil thickness of 18 microns was formed with through holes and component holes.Next, a catalyst treatment for chemical plating was performed. After that, a wiring pattern was formed by etching. The film-like material obtained in (2) was laminated onto the substrate using a laminator. After lamination.

After exposure to paper through a negative mask and then heating at 80° C. for 10 minutes, spray development was performed using 1,1,1-trichloroethane. (20℃, 80 seconds) After development, 80℃
It was dried at ℃ for 5 minutes and irradiated with light of 2.5 J/cd using a high pressure mercury lamp (80!1/aJ). Thereafter, heat treatment was performed at 150° C. for 30 minutes to form a protective film.

(4) Chemical copper plating Next, chemical copper plating bath (pH 12.5 (20℃), 60℃
℃) for 16 hours, and copper plating approximately 25 microns thick was applied to the through holes and component holes. After chemical copper plating treatment, rinse thoroughly with water and further heat at 80℃ for 10 minutes.
After drying for 1 minute, heat treatment was performed at 130°C for 60 minutes.

During this series of chemical copper plating treatments, no deterioration, peeling, blistering, etc. of the protective film occurred, and sufficient resistance was exhibited. Furthermore, neither penetration of the plating solution onto the copper wiring nor lifting of the protective film from the base material was observed.

Further, as a soldering heat resistance test, the protective film was immersed in a solder bath at 255 to 265° C. for 10 seconds, but the protective film was stable, and no cracking or peeling was observed, indicating that it was sufficiently useful as a solder mask.

Example 7 (1) Synthesis of epoxy acrylate 430 g (2 equivalents) of novolac type epoxy resin (EOCN-102, manufactured by Nippon Kayaku Co., Ltd., trademark, epoxy equivalent weight 215), 130 g (2 equivalents) of acrylic acid (1,8 parts 4i1), 240 g of tricrene Pour into an IQ flask, add 0.4 g (about 0.1%) of ρ-methoxyphenol as a polymerization inhibitor,
1.8 g (0.5%) of benzyldimethylamine was added and reacted at 90° C. for 5 hours. The end point of the reaction was determined by measuring the acid value using a conventional method, and was determined to be the point at which the value became 1 or less.

(2) Preparation of photosensitive resin composition solution Epoxy acrylate solution obtained in (1) above 75
Part trimethylolpropane triacrylate 10
Part methyl methacrylate/methacrylic r! I&/butyl methacrylic acid 45 parts 7 parts 1 part 0.1 part 5 parts 40 parts (weight ratio: 80/16/4) Copolymer (molecular weight approx. 15
0000) Benzophenone N,N-dimethylaminobenzophenone Hydroquinone Phthalocyanine compound represented by the following formula Methyl ethyl ketone A photosensitive resin composition solution having the above composition was prepared.

A protective film was formed on the substrate in the same manner as in Example 6 using this resin solution. Next, chemical copper plating was performed in the same manner as in Example 6. After this, sufficient water washing and drying were performed. During this series of chemical copper plating treatments, no deterioration, lifting, peeling, or penetration of the plating solution was observed in the protective film, indicating sufficient protection and adhesion to copper.

Example 8 (1) Synthesis of bisphenol-type epoxy acrylate Epicote 828 (manufactured by Yuka Shell Co., Ltd., trademark, epoxy equivalent: 190) 570 g (3 equivalents) and 201 g of acrylic acid
(2.8 mol) was placed in an IQ flask, 0.77 g (0.1%) of methoxyphenol and 3.9 g of benzylmethylamine were added as polymerization inhibitors, and the mixture was reacted at 90° C. for 6 hours. Thereafter, the acid value was measured by a conventional method, and the end point was when the value became 1 or less.

(2) Preparation of photosensitive resin composition solution Epoxy acrylate obtained in Example 7 (1) 90 parts (resin content 54 parts) Epoxy acrylate obtained in (1) above 20 parts p-methoxyphenol 0.1 part A protective film was formed on the substrate by carrying out the same operation as in Example 6 using the above composition of 2 parts of the phthalocyanine compound shown by the formula and 30 parts of trichlene. When the substrate was plated in the same manner as in Example 6, no deterioration, lifting, peeling, or penetration of the plating solution of the protective film was observed. After this.

Although soldering was performed, no change was observed in the protective film.

Example 9 (1) Synthesis of urethane acrylate Tolylene diisocyanate (TDI) 348 g (4 equivalents)
t), 475g of hydroxyethyl acrylate (4,
1 mole) and 549 g of methyl ethyl ketone were placed in a 2Q flask, and 1.6 g of zinc octylate (0
．． 2%) was added and reacted at 60°C for 8 hours.
The equivalent amount of NGO was measured by a conventional method, and the NC0 value was 0.
．． The end point of the reaction was set to 2 or less.

(2) Preparation of photosensitive resin composition solution Urethane acrylate of (1) above 40 parts (resin content 24 parts) Epoxy acrylate of Example 8
20 parts Methacrylic acid copolymer used in Example 6 30 parts 2-ethylanthraquinone
3 parts p-methoxyphenol
O, OS part Phthalocyanine compound used in Example 6 0.5 part Methyl ethylke 1-
28 parts The same operation as in Example 6 was performed using the above composition to form a protective film on the substrate.

When the substrate was chemically plated in the same manner as in Example 6, no deterioration, lifting, peeling, or penetration of the plating solution of the protective film was observed.

Example 10 (1) Synthesis of bisphenol-type epoxy acrylate ER332 (manufactured by Dow Chemical Company, epoxy equivalent: 330
) 173 g (1 equivalent) and 660 g of DER542 (manufactured by Dow Chemical Company, bromine content 46%, epoxy equivalent 330)
(2 equivalents) and 201 g (2.8 moles) of acrylic m were placed in an IQ flask, and 1.0 g of methoxyphenol was added.
(0.1%), benzylmethylamine 5.1g (0
, 5%) was added thereto, and the reaction was carried out at 90°C for 6 hours.

Epoxy acrylate was synthesized in the same manner as in Example 2 except for the above.

(2) Preparation of photosensitive resin composition solution 40 parts of urethane acrylate obtained in (1) of Example 9 (resin content 24 parts) Epoxy acrylate of above (1)
30 parts Methacrylic acid copolymer used in Example 7 35 parts Irgacure 907
4.5 parts p-methoxyphenol
0.1 part Phthalocyanine compound used in Example 6 3 parts Methyl ethyl ketone 46 parts A photosensitive resin composition solution was prepared according to the above composition, and a protective film was formed on the substrate in the same manner as in Example 6.

Next, chemical copper plating treatment was performed in the same manner as in Example 6, and no deterioration, lifting, peeling, or penetration of the plating solution of the protective film was observed. Subsequently, soldering was performed, but no change was observed.

Comparative Example 4 Preparation of photosensitive resin composition solution Epoxy acrylate obtained in Example 6 (1) 75 parts (resin content 45 parts) Trimethylolpropane triacrylate 10 parts Methacrylic acid copolymer used in Example 2 45 benzophenone
7 parts N,N-dimethylaminobenzophenone 1 part hydroquinone
o, i part methylene blue
5 parts A photosensitive resin composition solution having the above composition was prepared, and a protective film was formed on a substrate in the same manner as in Example 1.

Next, chemical steel plating was performed in the same manner as in Example 1. After this, sufficient water washing and drying were performed.

After chemical plating, no deterioration of the protective film itself was observed, but penetration of the plating solution onto the copper wiring and lifting of the protective film around the lands were observed. When the substrate was floated in a solder bath (260° C.) for 10 seconds, the protective film peeled off at the areas penetrated by the plating solution and at the floating areas.

Comparative Examples 5 to 9 Photosensitive resin composition solutions were prepared with the compositions shown in Table 1, and were formed as protective films on substrates in the same manner as in Example 6. After that, chemical copper plating and soldering were performed in the same manner as in Example 6.

The results are shown in Table 1.

This result shows that when the addition range of the phthalocyanine compound is out of the range defined in the present invention, the desired properties cannot be obtained.

〔Effect of the invention〕

As described above, according to the present invention, a silane coupling agent or a phthalocyanine compound is added to improve the adhesion of a photosensitive resin composition that can be used as a protective film for chemical plating and soldering to copper foil. Therefore, it is effective in preventing penetration of the plating solution onto the copper foil and lifting of the protective film during chemical plating.

Claims (1)

[Claims] (1) (a) Ethylenically unsaturated, containing at least two or more ethylenically unsaturated bonds, capable of forming a polymer in addition polymerization initiated by a photopolymerization initiator, and being liquid or solid at room temperature Compound. (b) a thermoplastic polymer compound; (c) a photopolymerization initiator that generates free radicals upon irradiation with actinic light; (d) a thermal polymerization inhibitor; (e) a silane coupling agent; A photosensitive resin composition for chemical plating, characterized in that it is added as an adhesion improver. (2) (a) Ethylenically unsaturated, containing at least two or more ethylenically unsaturated bonds, capable of forming a polymer in addition polymerization initiated by a photopolymerization initiator, and being liquid or solid at room temperature (b) a thermoplastic polymer compound, (c) a photopolymerization initiator that generates free radicals upon irradiation with actinic light, (d) a thermal polymerization inhibitor, and (e) a phthalocyanine compound. A photosensitive resin composition for chemical plating, characterized in that it is added as an adhesion improver.