JPS6224687A - Laminate board for chemical plating - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a laminate for chemical plating that improves and improves the solder heat resistance of a printed wiring board manufactured by an additive process. It features an adhesive layer formed on the laminate.

[Prior art]

Regarding the adhesive layer of a laminate for chemical plating, there are, for example, JP-A-58-140238 and JP-A-58-57776, which describe a method for manufacturing an adhesive and a method for forming an adhesive layer on an insulating substrate. is detailed.

When a phenolic resin-impregnated paper base material is heated and cured to form an insulating substrate, an adhesive layer is applied and dried on top of this, and a printed wiring board is manufactured using an additive process, the soldering heat resistance of the printed wiring board is relatively good. be. However, industrially, forming the adhesive layer is extremely complicated;
The surface of the chemical plating laminate on which the adhesive layer is formed has problems such as being easily contaminated by foreign matter and being susceptible to damage such as scratches.

In order to solve these problems, a method of manufacturing a chemical plating laminate by integral press molding is also well known.

In this case, conventional adhesives have a low level of soldering heat resistance for printed wiring boards using additive processes, making it difficult to put them into practical use.

Press integral molding involves stacking multiple sheets of phenolic resin-impregnated paper base material, and then coating both sides with a release sheet.
This is a method in which dried adhesive layers are overlapped and integrally molded, but in this method, condensation water from the curing reaction of the phenol resin is still contained in the laminate, so the chemical pressure caused by this press integral molding is When a laminate for plating is made into a syblint wiring board by an additive process, when the resulting printed wiring board is floated on molten solder, the condensed water vaporizes and diffuses outside the laminate, so chemical plating of the printed wiring board is difficult. The layers may peel off or become sticky. That is, laminates for chemical plating formed by integral press molding inherently have a drawback in that they have a low level of resistance to soldering heat, which is a subsequent process.

[Purpose of the invention]

The present invention improves the productivity of chemical plating laminates by integral press molding when manufacturing syblint wiring boards using an additive process, and also improves the soldering heat resistance of printed wiring boards. As a result of intensive studies to improve the soldering heat resistance, we found that it is possible to improve the soldering heat resistance by incorporating more anti-aging agents in the adhesive layer than usual and using a specific NBR rubber. This is what led to this.

[Structure of the invention]

The present invention provides a laminate for chemical plating having an adhesive/8 mainly composed of NBR rubber and a thermosetting resin, in which the adhesive layer contains 1 to 10% by weight of an anti-aging agent, and acrylonitrile NB with a content of 25 to 45% by weight
This is a laminate for chemical plating characterized by containing an R rubber component in an amount of 30 to 7 degrees.

The anti-aging agents used in the present invention include amine-based anti-aging agents, phenol-based anti-aging agents, benzimidazole-based anti-aging agents, etc. As the amine-based anti-aging agents, 6-nitoxy-1,2-dihydro- 21214-
trimethylquinoline, phenyl-1-naphthylamine,
Octylated diphenylamine, 4.4'-(α,α-dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylamide)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-
diphenyl-p-phenylenediamine, N-phenyl-
One or more types of N'-isopropyl-p-7 22-diamine and the like can be used.

As a phenolic anti-aging agent, 2,6-sheeter
t-Butyl-4-methylphenol, tri(α-methylbenzyl)phenol, 2-2'-methylenebis(4
-ethyl-6-tert-butylphenol), 4-4
One or more types of '-butylidene bis(3-methyl-6-tert-butylphenol) and the like can be used.

As the penzimidazole anti-aging agent, one or more of 2-mercazotobenzimidazole, 2-mercazotomethylbenzimidazole, zinc salt of 2-mercazotobenzimidazole, etc. can be used.

In addition, anti-aging agents such as dithiocarbamate-based and thiourea-based anti-aging agents can also be used.

As the anti-aging agent, an amine-based anti-aging agent is particularly preferable. The content of anti-aging agent in the NBR rubber component is 1~
It is 10%. If it is less than 1%, the effect in terms of heat resistance will be small, and if it exceeds 10%, deterioration will be observed in terms of bath agent resistance and electrical properties. Preferably it is 2 chill 5%.

Furthermore, the acrylonitrile content in the NBR rubber component is 2
It is 5 to 45 inches. If it is less than 25 inches, it cannot be used in terms of solvent resistance and heat resistance. If it exceeds 45%, it becomes difficult to roughen the surface of the adhesive layer using chromic acid/sulfuric acid during the additive process, resulting in poor layer density of chemical gold plating.

Preferably it is 35 to 40%. The content of NBR rubber in the adhesive is between 30 and 70%. If it is less than 30 inches, it is difficult to roughen the surface of the adhesive layer using chromic acid/sulfuric acid.

If it exceeds 70 inches, the adhesive will not cure sufficiently, and
Electrical properties also deteriorate. Preferably it is 50 inches to 60 inches.

〔Effect of the invention〕

A printed wiring board manufactured by an additive process using the chemical plating laminate of the present invention has solder + #I
Compared to chemical plating laminates made using the conventional press integral molding method, the heat resistance is extremely superior, and the reliability of the soldering process and the adhesion of chemical plating against long-term aging are also good. be.

In the present invention, the adhesive layer has extremely excellent solder heat resistance not only when formed by the press integral molding method but also when formed on a pre-formed insulating substrate,
It also has excellent electrical properties and chemical resistance.

〔Example〕

The chemical plating laminate of the present invention will be explained below using Examples and Comparative Examples. "Parts" represent "parts by weight" of gold.

Example 1 NBR rubber with acrylonitrile content of 35% 5
0 parts resol type phenolic resin
47 parts amine anti-aging agent
3 parts methyl ethyl ketone (solvent)
Mix 200 parts of the above liquid adhesion agent and form a layer with a thickness of 50 μm.
The film was coated and dried on a polymethylpentene film, and 8 sheets of phenolic resin-impregnated paper base material were laminated on both sides of the laminated material, and an adhesive layer was formed on both sides by heating and pressing with a press. A 6% chemical plating laminate was obtained.

The thickness of the adhesive layer was 30 μm.

Example 2 NBR rubber with acrylonitrile content of 40% 60
Part resol type phenolic resin 3
5 parts phenolic anti-aging agent
5 parts methyl ethyl ketone (solvent)
200 parts of the above-mentioned liquid adhesion agent was prepared, and the same procedure as in Example 1 was carried out to obtain a laminate for chemical plating having a thickness of 1.6%.

The thickness of the adhesive layer was 35 μm.

Example 3 The adhesive obtained in Example 2 was applied to both sides of a 1.5% thick phenol resin-impregnated paper base laminate and dried to obtain a laminate for chemical plating. The thickness of the adhesive layer was 30 μm.

Example 4 NBR rubber with acrylonitrile content of 40%
Part resol type phenolic resin 41
．． 5 Part amine anti-aging agent
3-part thiuram vulcanization accelerator
0.5 part silicon oxide fine powder
5 parts methyl ethyl ketone
200 parts of the above-mentioned liquid adhesion agent was prepared, and the same procedure as in Example 1 was carried out to obtain a laminate for chemical plating having a thickness of 1.6%.

The thickness of the adhesive layer was 30 μm.

Comparative Example 1 NBR rubber with acrylonitrile content of 40% 80
Part resol type phenolic resin 1
7-part amine anti-aging agent
3-part methyl ethyl ketone
200 parts of the above-mentioned liquid adhesion agent was prepared, and the same procedure as in Example 1 was carried out to obtain a laminate for chemical plating having a thickness of 1.6%.

The thickness of the adhesive layer was 35 μm.

Comparative Example 2 NBR rubber with acrylonitrile content of 20% 50
Part resol type phenolic resin 4
7-part amine anti-aging agent
3 parts methyl ethyl ketone 2
00 parts The above-mentioned liquid adhesion agent was prepared and carried out in the same manner as in Example 1 to obtain a laminate for chemical plating having a thickness of 1.6%.

The thickness of the adhesive layer was 30 capes.

Comparative Example 3 NBR rubber with acrylonitrile content of 30% 5
0 parts resol type phenolic resin 49
．． 5 Part amine anti-aging agent
0.5 parts methyl ethyl ketone
200 parts of the above-mentioned liquid adhesion agent were prepared and the same procedure as in Example 1 was carried out to obtain a laminate for chemical plating having a thickness of 1.6'%.

The thickness of the adhesive layer was 30 μm.

The 7L chemical plating laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to chemical copper plating by a well-known additive process to obtain printed wiring boards. Table 1 shows the characteristics of each printed wiring board. As is clear from Table 1, when the adhesive layer, which is a feature of the present invention, is formed, it has excellent solder heat resistance, which is an important property for printed wiring boards, and has extremely good electrical insulation and beer strength. be.

Claims (1)

[Claims] In a chemical plating laminate having an adhesive layer mainly composed of NBR rubber and a thermosetting resin, the adhesive layer contains 1 to 10% by weight of an anti-aging agent in terms of solid content,
and N with an acrylonitrile content of 25 to 45% by weight
A laminate for chemical plating characterized by containing 30 to 70% of a BR rubber component.