JPH0818224A - Adhesive for additive solder and manufacture of printed board using it - Google Patents

Abstract

PURPOSE:To provide additive plate adhesive which suppresses a through hole etch back quantity and solder quantity into the glass cloth layer of a substrate, improves adhesion with the solder film and solder heat resistance and allows KMnO4 roughening. CONSTITUTION:The major components of adhesive for additive solder are as follows: (a) Bisphenol A-type epoxy resin provided by adding isocyanate ethyl methacrylate to 20-100% of secondary hydroxyl group, (b) novolak epoxy resin provided by adding acrylic acid to 20-70% of epoxy group, (c) acrylonitrile- butadiene rubber provided by adding acrylic acid or methacrylic acid, (d) resol- type phenol resin, (e) photopolymerization initiator and (f) thermosetting agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive used for printed wiring boards by additive plating, and more particularly to KM.
The present invention relates to an adhesive for additive plating which can be roughened with an aqueous nO ₄ solution and a method for producing a printed wiring board using the same.

[0002]

2. Description of the Related Art As a (full) additive plating adhesive, a thermosetting adhesive containing an epoxy resin, acrylonitrile butadiene rubber (hereinafter abbreviated as NBR), and a resol type phenol resin as a main component has been known. .
Further, in JP-A-63-155793, a photo-curable adhesive film using a photosensitive diallyl phthalate resin and / or a photosensitive epoxy resin is used as an inner layer also as an insulating layer of a multilayer printed wiring board. A method of laminating on a wiring board is disclosed.

On the other hand, the applicant of the present invention has previously prepared a thermosetting epoxy resin, NBR, and a resole-type phenol resin as main components, and using a photocationic initiator as a curing agent for the epoxy resin to polymerize with light, An adhesive film for additive plating in which NBR and a phenol resin are crosslinked by heating has been proposed (JP-A-3-220281).

The above adhesive is applied on the surface of a glass epoxy substrate or laminated with a hot roll, irradiated with light and / or heat-cured before use. Then, after forming a through hole with a drill, the surface of the adhesive was roughened with a chromium sulfuric acid solution in order to secure adhesiveness with the electroless plating film.

However, in recent years, due to environmental problems, an alkaline permanganate aqueous solution as a roughening liquid other than the chromium sulfuric acid liquid,
For example, the KMnO ₄ solution has received attention. Originally KM
The nO ₄ solution has been used as a desmearing solution for the inner wall of the through hole, but this KMnO ₄ solution roughens the thermosetting adhesive for additive plating to improve the adhesion to the plating film. The method is Japanese Patent Publication No. 52-245.
No. 49 and Japanese Patent Laid-Open No. 53-88164.

[0006]

However, the present inventors have used many adhesives including the above-mentioned adhesives and used KMnO ₄
By changing the concentration, pH, temperature, and time of the solution, we examined the roughening of the adhesive layer for desmearing the inner wall of the hole and the adhesion with the plating film. I found the following problems that could not be solved.

(1) The amount of etch back of the inner wall of the through hole (dissolution of the epoxy resin layer on the inner wall of the through hole with the KMnO ₄ solution) and the adhesive strength of the plating film are not compatible with each other. That is, under the processing conditions of the KMnO ₄ solution for reducing the etch back amount, the adhesive layer cannot be roughened so much, and the adhesive force with the plating film is as low as about 1 kgf / cm. Further, the soldering heat resistance at 260 ° C. is as low as 30 seconds or less. Adhesion with the plating film is 1.
Under the KMnO ₄ treatment condition of 5 kgf / cm 2 or more, the etching back amount of the inner wall of the through hole increases to 10 μm or more, and the amount of penetration of the plating film into the glass cloth layer is 15
Larger than μm. Furthermore, the solder heat resistance is low.

(2) The adhesive force with the plating film is 2 kgf /
After roughening the adhesive layer under the treatment conditions of the KMnO ₄ solution that can secure about cm, and performing a series of treatments such as applying and activating a plating catalyst, a diluted alcohol-based development type dry film plating resist is formed, When exposed and developed, the adhesive strength of the plating film becomes 0.8 kgf / cm or less, and the solder heat resistance also becomes 10 seconds or less. This is because the surface of the conventional adhesive layer roughened with the KMnO ₄ solution is deteriorated by the diluted alcohol type developer of the plating resist.

As described above, it has been found that there are many problems to be solved in roughening a conventional adhesive with a KMnO ₄ solution to produce an additive-type printed wiring board.

An object of the present invention is to provide a novel KMnO ₄ rough film which can suppress the amount of etch back of the inner wall of the through hole and the amount of penetration of the plating film into the glass cloth layer, and improve the adhesion to the plating film and the solder heat resistance. An object of the present invention is to provide an adhesive for adhesive plating and a method for producing a printed wiring board using the same.

[0011]

Means for Solving the Problems The gist of the present invention for solving the above problems is as follows.

(A) Bisphenol A type epoxy resin in which isocyanatoethyl methacrylate is added to 20 to 100% of secondary hydroxyl group, (b) 20 to 70 of epoxy group
% Novolac type epoxy resin with acrylic acid added,
(C) Acrylonitrile-butadiene rubber to which acrylic acid or methacrylic acid is added, (d) a resole-type phenol resin, (e) a photopolymerization initiator, and (f) an adhesive for adhesive plating containing a thermosetting agent as a main component.

Furthermore, (a) + (b) is 40 to 15 parts by weight of component (c) with respect to 60 to 85 parts by weight of (a) +.
(D) is 1 to 1 with respect to 100 parts by weight of (b) + (c)
0 parts by weight.

The average epoxy equivalent of the bisphenol A type epoxy resin to which isocyanatoethyl methacrylate (a) is added is preferably 450 to 4000. When the epoxy equivalent is less than 450, the KMnO ₄ solution is likely to be roughened, but the heat resistance is poor, and the plating resist is easily dissolved in the developing solution in the developing process. If it exceeds 4000, it cannot be roughened with the KMnO ₄ solution.

The average epoxy equivalent of the novolac type epoxy resin added with acrylic acid (b) is from 200 to 500.
Are preferred. If it is less than 200, it is easily roughened by the KMnO ₄ solution, but it is easily dissolved in the developing solution in the development processing of the plating resist. If it exceeds 500, the cured product becomes brittle and the roughening property is not improved.

Acrylonitrile butadiene rubber (NB) to which acrylic acid or methacrylic acid is added (c)
R) is for imparting flexibility to the cured product and improving the adhesiveness with the plating film.

The resol type phenolic resin (d) is a cross-linking agent for the NBR (c), and the alkyl-modified type is particularly preferable from the viewpoint of improving reactivity.

The photopolymerization initiator of the above (e) is (a),
(B), (c) Photosensitive group photosensitizing group, known as benzophenone, benzyl dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropane-1 The radical generator can be used.

As the heat curing agent (f), an amine curing agent represented by dicyandiamide or an imidazole curing agent can be used.

Next, the compounding amounts of the respective components (a) to (f) will be described.

(A) + (b) is 60 to 85 parts by weight, but the compounding ratio of both is (a) 10 to 30 parts by weight, (b)
30 to 75 parts by weight is preferable from the viewpoint of roughening property by the KMnO ₄ solution and heat resistance. As the component (a), it is not preferable to add more than 30 parts by weight of those having an epoxy equivalent of 2000 or more, since the roughening property of the KMnO ₄ solution will be deteriorated.

The compounding amount of (c) is 15 to 40 parts by weight, but when it is less than 15 parts by weight, the adhesiveness of the plating film becomes 1 or less. If it is more than 40 parts by weight, the heat resistance will decrease.

The compounding amount of (d) is (a) + (b) +
It is 1 to 10 parts by weight with respect to 100 parts by weight of (c), but if it is less than 1 part by weight, the crosslink density with NBR will be low and the heat resistance will be reduced. If it exceeds 10 parts by weight, the roughening property with the KMnO ₄ solution is lowered.

(E) is (a) + (b) + (c) no 10
3 to 10 parts by weight is sufficient with respect to 0 parts by weight.

In (f), the compounding amount is determined according to the epoxy equivalent and compounding amount of the epoxy resin used, and the curing speed.

Each of the above components is dissolved in a ketone or cellosolve organic solvent and used as a liquid. In addition, silicon oxide, aluminum oxide, calcium silicate, aluminum hydroxide, calcium hydroxide, zinc oxide, compounding a fine powder filler such as magnesium oxide according to the purpose, knife coatability, roll coatability, curtain coatability, The required rheology such as screen printability and spray coatability can be imparted depending on the type of coat. These fine powder fillers are kneaders, three rolls,
Alternatively, it can be uniformly dispersed by various ball mills.

It goes without saying that defoaming agents such as silicone oil and leveling agents can be added.

The adhesive is coated and formed, for example, on the surface of a glass epoxy substrate or the surface of a so-called insulating shield multilayer plate on which inner layer wiring is formed and shielded by a prepreg. After drying the solvent, it is irradiated with 0.5-2 J / cm ² ultraviolet rays, and further 140-160 ° C., 20-60 in a heating and curing furnace.
Heat for a minute to cure. After forming the adhesive layer as described above, a printed wiring board can be manufactured by a known additive method.

A feature of the present invention is that after forming a through hole with a drill, desmearing in the through hole and roughening of the surface of the adhesive layer can both be achieved. That is, the KMnO ₄ concentration is 40 to 120 g / l, the pH is 12 to
14 (at 25 ° C) and a wide temperature range of 50 to 70 ° C,
By performing the treatment for 2 to 10 minutes, desmear and roughening can be performed at once. After the roughening, a printed wiring board can be prepared by a known method such as washing with water, neutralization treatment, plating catalyst application, activation, drying, plating resist formation, exposure, development, electroless plating and post curing.

[0030]

The function of the adhesive for additive plating of the present invention is KMn.
Even if roughened with O ₄ solution, the adhesive force with the plating film is 1.2 to 1.
It shows 8 kgf / cm and has a soldering heat resistance of 260 ° C. for 60 seconds or more, and the adhesive strength of the plating film and the soldering heat resistance are hardly deteriorated by resist development unlike conventional adhesives.

Further, the etch back amount of the inner wall of the through hole due to the roughening of the KMnO ₄ solution is 2 to 7 μm, and the amount of the plating film soaking into the glass cloth layer of the substrate is 10 μm or less.

Particularly, the average epoxy equivalent is 450 to 4000.
By using the bisphenol A type epoxy resin and the novolak type epoxy resin having an average epoxy equivalent of 200 to 500 in combination, it can be sufficiently roughened with an aqueous KMnO ₄ solution and has excellent developer resistance.

Further, the above-mentioned photocurable bisphenol A
-Type epoxy resin is different from the widely used epoxy group to which (meth) acrylic acid is added, in that the epoxy group remains at the terminal, and the novolac type epoxy resin also leaves the epoxy group. Therefore, it is presumed that the heat resistance is not impaired by the polymerization of the epoxy group with the thermosetting agent. Therefore, the above-mentioned relatively gentle KM
Since it can be sufficiently roughened even by roughening with the nO ₄ solution, it is considered that the amount of etch back of the inner wall of the through hole and the amount of penetration of the plating film into the glass cloth layer are reduced.

[0034]

【Example】

[Example 1] 30 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent 900) in which isocyanatoethyl methacrylate was added to 20% of secondary hydroxyl groups, and a cresol novolac type epoxy resin in which acrylic acid was added to 20% of epoxy groups ( Epoxy equivalent 230) 55 parts by weight, 15 parts by weight of NBR added with acrylic acid, 1 part by weight of alkyl-modified resol-type phenol resin, 6 parts by weight of benzyl dimethyl ketal as a photopolymerization initiator, 3 parts by weight of dicyandiamide-modified imidazole as a thermosetting agent, As a fine powder filler, an adhesive consisting of 5 parts by weight of silicon oxide, 5 parts by weight of talc, 20 parts by weight of calcium silicate, and 70 parts by weight of a mixed solvent of methyl ethyl ketone and methyl cellosolve was prepared.

The above adhesive is applied to the surface of an insulating shield plate having a prepreg laminated on the surface of the inner layer wiring with an applicator so that the thickness after drying becomes about 30 μm, and the adhesive is applied at 90 ° C. for 3 hours.
Dry for 0 minutes. Ultraviolet rays with high pressure mercury lamp of 1.5 J / cm ²
After irradiation, it was cured at 145 ° C. for 35 minutes. Then, two test pieces having through holes formed at predetermined positions were produced with a drill having a diameter of 35 μm. This was mixed with KMnO ₄ aqueous solution (concentration 120 g / l, pH 12.5, temperature 70 ° C.) 5
After roughening for 1 minute, washing with water, neutralization treatment, washing with water, plating catalyst treatment, washing with water, activation, and washing with water were carried out in order, and then 120
It was dried at ° C.

On one sheet, a plating film having a thickness of about 25 μm was formed using an electroless copper plating solution for additive. This is designated as a test piece (A). The other sheet was laminated with a dry film type plating resist, and the pattern was exposed, developed and washed with water. The developing solution at this time was 180 ml / l of diethylene glycol monobutyl ether and 5 g / l of sodium borax.
Spray development was carried out at 40 ° C. for 60 seconds with an aqueous solution consisting of Then, similarly to the sample (A), a plating film having a thickness of about 25 μm was formed with an electroless copper plating solution. This is designated as a test piece (B).

Next, both of them were post-cured at 160 ° C. for 40 minutes. Adhesion strength between plating film and adhesive layer is determined by JI
It was measured by the SC-6841 method. Specimen (A) is 1.18k
The gf / cm and the sample (B) showed 1.21 kgf / cm. Further, both of the 260 ° C. solder heat resistances showed 90 seconds or more.

Furthermore, as a result of observing the cross section of the through-hole portion, the etch back amount was 2 to 5 μm, and the penetration amount of the plating film into the glass cloth layer was 4 to 7 μm in both, and there was not much difference between them. I couldn't do it.

Example 2 10 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent 450) in which isocyanatoethyl methacrylate was added to 50% of secondary hydroxyl groups,
Cresol novolac type epoxy resin (epoxy equivalent 500) in which acrylic acid is added to 40% of epoxy groups 50
Parts by weight, 40 parts by weight of acrylic acid-added NBR, 10 parts by weight of alkyl-modified resol-type phenol resin, 6 parts by weight of benzyl dimethyl ketal as a photopolymerization initiator, 3 parts by weight of dicyandiamide-modified imidazole as a thermosetting agent, and oxidation as a fine powder filler. An adhesive consisting of 5 parts by weight of silicon, 5 parts by weight of talc, 20 parts by weight of calcium hydroxide and 500 parts by weight of a mixed solvent of methyl ethyl ketone and xylene was prepared.

On the surface of the same insulating shield plate as in Example 1,
The adhesive was applied with a curtain coater so that the thickness after drying was about 30 μm, and dried at 80 ° C. for 50 minutes. After irradiating this with high pressure mercury lamp of ultraviolet rays at 1.3 J / cm ² ,
It was cured at 150 ° C. for 30 minutes. Then, after forming a through hole with a drill as in Example 1, a series of treatments including roughening with a KMnO ₄ aqueous solution, electroless copper plating, or a plating resist to form electroless copper plating and post-curing were performed. However, the KMnO ₄ aqueous solution has a concentration of 50 g / l and a pH.
The test was carried out for 3 minutes using a temperature of 13.0 and a temperature of 50 ° C.

The adhesive force between the plating film and the adhesive was 1.78 kgf / cm for the sample (A) and 1.69 k for the sample (B).
It showed gf / cm. The solder heat resistance at 260 ° C. was 60 seconds or more in both cases. Further, as a result of observing the cross section of the through hole portion, the etch back amount of both is 3 to 5 μm,
The amount of penetration of the plating film into the glass cloth layer is 4 to 8 μm.
There was not much difference between the two in the range of.

Example 3 10 parts by weight of a bisphenol A type epoxy resin (epoxy equivalent 4000) in which isocyanatoethyl methacrylate was added to 100% of secondary hydroxyl groups, and cresol novolak type in which acrylic acid was added to 70% of epoxy groups Epoxy resin (epoxy equivalent 230)
60 parts by weight, 30 parts by weight of NBR added with methacrylic acid and a carboxyl group, 5 parts by weight of alkyl-modified resol type phenol resin, 2-methyl-1- as a photopolymerization initiator
4 parts by weight of [4- (methylthio) phenyl] -2-monforinopropane-1, 5 parts by weight of dicyandiamide-modified imidazole as a thermosetting agent, 5 parts by weight of silicon oxide as a fine powder filler, 5 parts by weight of talc, calcium carbonate 20
Part by weight, mixed solvent of methyl ethyl ketone and xylene 70
An adhesive consisting of 0 parts by weight was prepared.

As in Example 1, the adhesive was coated on the surface of the insulating shield plate with a curtain coater so that the thickness after drying was about 30 μm, and dried at 80 ° C. for 60 minutes. Next, after irradiating with ultraviolet rays at 1.3 J / cm ² with a high pressure mercury lamp,
It was cured at 150 ° C. for 30 minutes. After forming a through hole in this, a series of treatments from roughening with a KMnO ₄ aqueous solution, electroless copper plating, or forming a plating resist to perform electroless copper plating and post-curing were performed. However, the KMnO ₄ aqueous solution was treated for 10 minutes at a concentration of 70 g / l, a pH of 14.0 and a temperature of 60 ° C.

The adhesive force between the plating film and the adhesive layer was 1.54 kgf / cm for the sample (A) and 1.53 k for the sample (B).
It showed gf / cm. Both of the 260 ° C. solder heat resistances showed 90 seconds or more. Further, as a result of observing the cross section of the through hole portion, both had an etch back amount of 5 to 7 μm, and the amount of penetration of the plating film into the glass cloth layer was in the range of 6 to 9 μm.

Comparative Example 1 35 parts by weight of a bisphenol A type epoxy resin having an epoxy equivalent of 450, 40 parts by weight of acrylonitrile butadiene rubber, 25 parts by weight of an alkyl-modified resol type phenol resin, and hexafluoroantimony as a photocationic polymerization initiator of an epoxy resin. Adhesion of 2 parts by weight of acid triphenylsulfonium salt, 2 parts by weight of zinc oxide as a vulcanization aid, 2 parts by weight of silicon oxide as a fine powder filler, 5 parts by weight of talc, and 20 parts by weight of calcium hydroxide and having a thickness of 30 μm The agent film was laminated on the same insulating shield plate as in Example 1 by a hot roll of 120 ° C., irradiated with ultraviolet rays of 1.5 J / cm ² , and then at 150 ° C. for 3 minutes.
Cured for 0 minutes. Then, similar to Example 1, a through hole was formed.

Chromic anhydride 100 g /
1 and a sulfuric acid 200 ml / l roughening solution at 40 ° C. for 5 minutes, and a series of treatments was carried out in the same manner as in Example 1 to perform electroless copper plating. Adhesive strength is 2.53 kg for the test piece (A)
f / cm, the sample (B) showed 2.49 kgf / cm.

The solder heat resistance was 90 seconds or more. The amount of etch back of the inner wall of the through hole was 7 to 13 μm, and the amount of penetration into the glass cloth layer was 12 to 18 μm.

On the other hand, this adhesive was mixed with a KMnO ₄ concentration of 70 g.
/ L, pH 14.0, 50 ° C, roughening was performed for 5 minutes, and the same electroless copper plating as in Example 1 was performed. As a result, the surface of the adhesive was not roughened and the plating film was bulged. Therefore, the adhesive strength and solder heat resistance could not be measured.

Therefore, the temperature is adjusted to 70 with the same KMnO ₄ solution.
As a result of conducting roughening at 30 ° C. for 30 minutes, the adhesive strength of the test piece (A) was 1.13 kgf / cm, but the adhesive strength of the test piece (B) after the plating resist was formed was 0.1. 26 kg
It fell to f / cm.

The solder heat resistance was 23 seconds for the sample (A) and 6 seconds for the sample (B). The etch back amount of the inner wall of the through hole is 15 to 21 μm for both,
The amount of soaking into the glass cloth layer was also large, 19 to 33 μm.

The concentration of KMnO ₄ solution is 120 g / l,
The adhesive strength of the test piece (A) was 2.23 kgf / cm as a result of evaluation by adjusting the pH to 12.5 and roughening at 70 ° C. for 15 minutes.
However, the sample (B) which was formed by forming a plating resist and developed decreased to 1.02 kgf / cm.

The solder heat resistance of the sample (A) was 26 seconds, but that of the sample (B) was 3 seconds. The amount of etch back of the inner wall of the through hole was 13 to 18 μm for both, and the amount of penetration into the glass cloth layer was 15 to 28 μm.

Comparative Example 2 20 parts by weight of bisphenol A type epoxy resin having an epoxy equivalent of 900, 50 parts by weight of acrylonitrile butadiene rubber, 30 parts by weight of alkyl-modified resol type phenolic resin, and 8 parts by weight of dicyandiamide as a heat curing agent for epoxy resin. Curing an adhesive composed of 5 parts by weight of zinc oxide as a vulcanization aid, 2 parts by weight of silicon oxide as a fine powder filler, 20 parts by weight of aluminum hydroxide, 10 parts by weight of calcium carbonate, and 600 g of a mixed solvent of methyl ethyl ketone and xylene. Coat
The thickness of the adhesive after drying was set to 32 μm, and the adhesive was dried at 120 ° C. for 60 minutes and then heat-cured at 165 ° C. for 90 minutes to form through holes.

Chromic anhydride 60 g /
l, sulfuric acid 200 ml / l was used for roughening at 40 ° C. for 7 minutes, and a series of treatments were performed in the same manner as in Example 1 to perform electroless copper plating. The adhesive strength is 2.30 for the test piece (A).
kgf / cm, and the sample (B) showed 2.21 kgf / cm.

The solder heat resistance was 90 seconds or more. The amount of etch back of the inner wall of the through hole was 6 to 15 μm, and the amount of penetration into the glass cloth layer was 15 to 20 μm.

On the other hand, the same KMn as in Comparative Example 1 was used for this adhesive.
Roughening was performed at an O ₄ concentration of 70 g / l, pH 14.0, 50 ° C. for 5 minutes, and further electroless copper plating was performed as in Example 1. As a result, the surface of the adhesive was not roughened and the plating film was bulged. Therefore, the adhesive strength and solder heat resistance could not be measured.

Therefore, with the same KMnO ₄ solution, the temperature is adjusted to 70
As a result of roughening at 30 ° C. for 30 minutes, the adhesive strength of the test piece (A) was 0.98 kgf / cm, and the adhesive strength was 0.98 kgf / cm. 17 kg
It fell to f / cm.

The solder heat resistance was 28 seconds for the sample (A) and 5 seconds for the sample (B). The amount of etch back of the inner wall of the through hole was 13 to 18 μm, and the amount of penetration into the glass cloth layer was 22 to 26 μm.

Further, the concentration of KMnO ₄ solution is 120 g / l,
As a result of performing the roughening at 70 ° C. for 15 minutes with the pH of 12.5, the adhesive strength of the sample (A) was 2.03 kgf / cm.
However, the sample (B), which was formed by forming a plating resist and then developed, dropped to 0.98 kgf / cm.

The solder heat resistance of the sample (A) was 30 seconds, but that of the sample (B) was 7 seconds. The amount of etch back of the inner wall of the through hole was 14 to 20 μm, and the amount of penetration into the glass cloth layer was 23 to 31 μm.

[0061]

According to the present invention, the desmear treatment of the through hole with the KMnO ₄ solution and the roughening of the surface of the adhesive capable of improving the adhesive strength of the plating film can be achieved, and the amount of etch back of the inner wall of the through hole can be improved. In addition, the amount of plating soak into the glass cloth layer can be reduced. As a result, the inter-layer electrolytic corrosion resistance of the printed wiring board is excellent, and the pitch between the through holes can be narrowed.

Further, as an adhesive, a bisphenol A type epoxy resin having a relatively large epoxy equivalent and having a photosensitive group attached to a secondary hydroxyl group to leave an epoxy group, and a novolac type epoxy resin having an epoxy group similarly left By using the resin together, an adhesive layer having a Tg of 100 to 140 ° C. can be obtained. This improves the solder heat resistance and the repair resistance of the surface mount component.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Takahashi 7-1-1 Omika-cho, Hitachi City, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Toshinari Takada 1 Horiyamashita, Hadano City, Kanagawa Stock Company General Manager Computer Division, Hiritsu Factory (72) Inventor Shiro Kobayashi 1st Horiyamashita, Hadano City, Kanagawa Prefecture

Claims (6)

[Claims] 1. A bisphenol A type epoxy resin obtained by adding isocyanatoethyl methacrylate to 20 to 100% of a secondary hydroxyl group, and (b) 20 to 70 of an epoxy group.
% Novolac type epoxy resin with acrylic acid added,
An adhesive for additive plating containing (c) acrylonitrile-butadiene rubber to which acrylic acid or methacrylic acid is added, (d) a resole-type phenol resin, (e) a photopolymerization initiator, and (f) a thermosetting agent. 2. Among the components of the adhesive, (a) + (b) is 60 to 85 parts by weight, (c) is 40 to 15 parts by weight, and (a) + (b) + (c). The adhesive for additive plating according to claim 1, wherein 1 to 10 parts by weight of (d) is blended with 100 parts by weight of the above. 3. The average epoxy equivalent of the bisphenol A type epoxy resin added with (a) isocyanatoethyl methacrylate is 450 to 4000, and the average epoxy equivalent of the novolak type epoxy resin added with (b) acrylic acid is The adhesive for adhesive plating according to claim 1 or 2, wherein the resol type phenolic resin of 200 to 500, (d) is an alkyl-modified type. 4. An adhesive is applied to the surface of the substrate and cured,
A step of forming through holes at predetermined places, a step of roughening the adhesive surface and the inner walls of the through holes with a roughening solution, a step of forming a plating resist corresponding to a desired circuit pattern, a plating on the circuit patterns and the inner walls of the through holes. In a method for producing a printed wiring board, which comprises a step of applying a catalyst and activating, and a step of plating by electroless plating, the adhesive has added isocyanatoethyl methacrylate to 20 to 100% of the secondary hydroxyl group (a). Bisphenol A type epoxy resin, (b) epoxy group 20 to 70
% Novolac type epoxy resin with acrylic acid added,
(C) Acrylonitrile butadiene rubber to which acrylic acid or methacrylic acid is added, (d) resole type phenol resin, (e) photopolymerization initiator, (f) thermosetting agent as main components, and the roughening liquid is KMnO ₄ A method for producing a printed wiring board, which is an aqueous solution containing. 5. Among the components of the adhesive, (a) + (b) is 60 to 85 parts by weight, (c) is 40 to 15 parts by weight, and (a) + (b) + (c). The method for producing a printed wiring board according to claim 4, wherein (d) is compounded in an amount of 1 to 10 parts by weight per 100 parts by weight of. 6. The average epoxy equivalent of the (a) bisphenol A type epoxy resin added with isocyanatoethyl methacrylate is 450 to 4000, and the average epoxy equivalent of the acrylic acid added novolak type epoxy resin of (b) is The method for producing a printed wiring board according to claim 4 or 5, wherein the resol type phenolic resin of 200 to 500, (d) is an alkyl-modified type.