JPS6266935A - Manufacture of laminated 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] [Industrial Field of Application] The present invention relates to a method for manufacturing a laminate for chemical plating, and includes an adhesive layer formed on a release sheet on the surface of a thermosetting resin-impregnated base material. After stacking them together and integrating them by heating and pressing,
We produce laminates for chemical plating in which the release sheet adheres uniformly to the substrate surface, the sheet surface is smooth, the adhesive layer has excellent heat resistance, and the release sheet can be easily peeled off. It's about how to do it.

[Prior art]

Manufacturing a chemical plating laminate by superimposing an adhesive layer formed on a release sheet on the surface of a semi-cured thermosetting resin-impregnated base material and molding under heat and pressure is as follows:
This is already a known technique. In such a manufacturing method,
For example, in JP-A-52-121775, a technology to use aluminum foil as a release sheet was introduced in JP-A-58-1.
No. 99151 provides a technology for depressurizing in hot pressure molding.

When the thermosetting resin is an epoxy resin, less unreacted low-molecular gas is generated during hot-pressure molding, and the release sheet is uniformly and smoothly adhered to the thermosetting resin-impregnated base material. However, if the base material contains a solvent, or if the thermosetting resin is a phenolic resin, unreacted low-molecular gas may be released during hot-pressure molding. Since a large amount of is generated, the boat-shaped sheet partially floats when the heating and pressure forming is completed. Regarding the problem of chemical plating laminates where the release sheet is partially lifted, Japanese Patent Application Laid-Open No. 58-1991
51. In order to solve this problem,
In JP-A-58-199151, depressurization is performed during hot-press molding, but depressurization instantly generates a large amount of unreacted low-molecular gas, which is extremely dangerous in terms of work safety. In addition, sometimes the chemical plating laminate itself may break between the layers.

[Purpose of the invention]

The present inventors have conventionally discovered that when the surface K of a thermosetting resin-impregnated base material and the adhesive I- formed on a release sheet are superimposed and heated and press-molded, the release sheet is attached to the base material. This solves the drawbacks of not adhering uniformly and smoothly and causing wrinkles on partially lifted υ releasable sheets, and also improves the heat resistance of one adhesive layer and the adhesion of plating with the adhesive layer. Furthermore, in order to improve the releasability of the release sheet, it is effective to use a specific acrylonitrile butadiene rubber in the adhesive layer and a plastic film with an aluminum layer on the surface as the release sheet. After gaining knowledge of
This completes the present invention.

[Structure of the invention]

The present invention provides a method for manufacturing a laminate for chemical plating, in which an adhesive layer formed on a release sheet is superimposed on the surface of a plurality of semi-cured thermosetting resin-impregnated base materials, and the adhesive layer is formed under heat and pressure. , the adhesive layer contains partially crosslinked acrylonitrile butadiene rubber and a thermosetting resin, and at least one surface of a plastic film with a melting point of 200° C. or higher is vapor-deposited with aluminum as a release sheet;
Alternatively, there is a method for producing a laminate for chemical plating, characterized in that a composite sheet gold releasable sheet is laminated with an aluminum foil having a thickness of 1 to 25 μm.

In the present invention, the adhesive layer formed on the release sheet is mainly composed of acrylonitrile butadiene rubber (hereinafter referred to as NBR) and a thermosetting resin. It is crosslinked. Partially crosslinked NBR has poor compatibility with solvents and thermosetting resins as it is, but by mastication, a part of the crosslinks are cut and this part becomes reactive, and at the same time,
Becomes compatible with solvents and thermosetting resins.

Such NBR is mixed with a thermosetting resin and a solvent, applied to a release sheet, and dried.

Thereafter, it is laminated with a plurality of thermosetting resin-impregnated substrates and heated and pressed. At this time, the NBR in the adhesive layer and the thermosetting resin react, and the heat resistance of the adhesive layer is improved. On the other hand, this reaction tends to increase the adhesion to the releasable sheet, but in this case, the releasability can be improved by adding a phospholipid body. Furthermore, the use of partially crosslinked NBH improves the adhesion between the adhesive layer and the plating metal when chemically plated.

Next, the plastic film used in the present invention with a melting point of 200°C or higher is polyethylene terephthalate,
The film is made of d-trimethylintene, polysulfone, halether sulfone, selistyrene, ytrlJ carbonate, triacetate, yriether ether ketone, etc.

From the viewpoint of heat resistance, polyethylene terephthalate, I-licarbonate, triacetate, and polymethylinthene are particularly preferred as plastic films with high melting points.

The thickness of the plastic film is usually 10 μm or more and 100 μm or less, preferably 25/jm or more and 60 μm or less, in view of the thermal and mechanical properties required during adhesive layer formation and integral molding by pressure heating. It is as follows.

The plastic film has air permeability when heated at 150 to 180° C., and unreacted low molecular gas and condensed water that diffuse and evaporate from within the substrate can easily pass therethrough.

Aluminum evaporation molded into plastic film
Regarding the thickness, it is usually possible to use a thickness of 1 μm or less, but from the viewpoints of air permeability, uniformity of the deposited layer, and cost, 1 μm or less can be used.
Particularly preferred is oA~1000 people. By providing this aluminum vapor deposited layer, the peel strength between the adhesive layer and the release sheet is 50% regardless of the properties of the plastic film.
~tsof/country, which is approximately constant, and the releasable sheet can be molded into an apparently fixed state. If only a plastic film is used, it will float or, conversely, it will adhere to such an extent that it cannot be easily peeled off. That is, it is only necessary to control the affinity and adhesion between the aluminum vapor deposited layer and the adhesive layer, regardless of the strength of the chemical affinity between the adhesive layer and the surfaces of various plastic films.

In addition, if the heat resistance of the plastic film is insufficient in relation to the heating and pressurizing conditions, it is necessary to reduce the thickness of the aluminum vapor-deposited layer, especially from the viewpoint of dimensional change and mechanical strength when heated. Heat resistance can be improved by laminating and reinforcing aluminum foil with a thickness of 1 to 25 μm. The thickness of the aluminum foil to be laminated is preferably 5 μm to 10 μm from the viewpoint of air permeability and lamination workability.

In addition, if the plastic film comes into direct contact with the end plate of the press after heating and pressure forming and contaminates the end plate, use a plastic film with aluminum vapor-deposited on both sides, or a plastic film with aluminum vapor-deposited on one side and a thick film on the other side. Sa1~
By using a plastic film laminated with 25 μm aluminum foil or a plastic film laminated with the above-mentioned aluminum foil on both sides as a release sheet, it is possible to avoid contamination during contamination. gt - can be solved.

Next, the adhesion between the adhesive layer and the release sheet will be explained. This adhesion varies depending on the S type of NBR, the blending ratio of adhesive components, the amount of unreacted low molecular gas or condensed water generated, press heating and pressure molding conditions, etc.

Regarding the type of NBR, as mentioned above, partially cross-linked NBR
BR rubber has strong adhesion, and regarding press heating and pressure molding conditions, the higher the heating temperature and the longer the heating time, the stronger the adhesion.

If the releasable sheet is highly adhesive and difficult to peel off, the releasability can be improved by adding a phospholipid body to the adhesive. As the phospholipid body, phosphatidic acid, phosphatidylcholine, phosphatidylethanolamine, plasmalogen, etc. can be used. The addition value of phospholipid body is 0.01 of the N amount ratio in the solid content of the adhesive.
~5. A sufficient effect is obtained at 0%. Preferably 0.1~
It is 2.5%.

〔Effect of the invention〕

According to the present invention, it is possible to diffuse and evaporate the unreacted low-molecular gas or water vapor caused by condensed water, which is often generated in a curable resin-impregnated base material, onto the outer surface of the base material without retaining or containing it in the base material. At the same time, since the melting point of the release sheet is high, there is little damage due to thermal deterioration, and the sheet can be integrally molded while maintaining uniform appearance and smoothness. Furthermore, when peeling off a K-type releasable sheet used as a laminate for chemical plating, it is possible to do so without causing tears or cracks. Furthermore, the adhesive surface of the chemical plating laminate and the press head plate will not be contaminated by impurities and additives IK eluted from the template sheet itself, and the release sheet will not adhere to the press head plate.
There are no problems with poor adhesion during the plating process or press molding.

Since the heat resistance of the adhesive layer is improved, the adhesive layer is not deteriorated by various treatments during chemical plating, and its adhesion to the plated metal is improved.

〔Example〕

The method for producing a laminate for chemical plating according to the present invention will be explained below using Examples and Comparative Examples.

The part indicates the it part.

First, an adhesive with the following formulation was prepared.

Partially crosslinked NBR (Japanese Synthetic Rubber N-210S) 10
0 parts resol type phenolic resin 100 parts phosphatidic acid 5 parts Solvent (methyl ethyl ketone > 5oon) Example 1 Pyrimethylpentene (T
PX) An aluminum vapor deposition layer with a thickness of 500 mm is formed on one side of the film, and the NBR/
Coating an adhesive mainly composed of phenolic resin, 160
℃ for 30 minutes to remove the solvent and pre-air the adhesive layer to the B stage state, each layer having a thickness of 50 μm.
A releasable sheet having an adhesive layer was obtained. An adhesive layer formed on the aluminum-deposited side of the pyrimethylinten film is applied to both sides of the paper base material impregnated with phenolic resin. They were kneaded together and heated and cured by pressing at 170° C. for 120 minutes to obtain a chemical plating laminate with a release sheet attached.

Example 2 A laminate for chemical plating was obtained in the same manner as in Example 1 by forming a 500-layer aluminum vapor deposited layer on both sides of a T, 617 carbonate (PC) film with a melting point of 240° C. and a thickness of 60 μm. .

Example 3 A 10 μm thick aluminum foil was laminated on one side of a 50 μm thick triacetate film with a melting point of 290° C.) L,
3 with 500 aluminum evaporated layers formed on another side
A laminate for chemical plating was obtained in the same manner as in Example 1, using a layered composite sheet as a release sheet.

Example 4 A three-layer composite sheet with a melting point of 240° C. and a 40 μm thick pyristyrene film laminated with 10 μm thick aluminum foil on both sides was used as a release sheet, and chemical plating was performed in the same manner as in Example 1. A laminate for use was obtained.

Example 5 An aluminum vapor-deposited layer with a thickness of 500 mm was formed on both sides of a PET film with a melting point of 260° C. and a thickness of 50 μm, and the composite film was used as a release sheet. A chemically plated laminate was obtained in the same manner as in 1.

Example 6 A laminate for chemical plating was produced in the same manner as in Example 1, except that a Nyxi resin-impregnated glass substrate with a solvent content of 3% was used as the glue for the phenol resin-impregnated paper substrate. Obtained.

Comparative Example 1 NIJ Methyl R-Ntenthene (melting point 240°C, thickness 50 μm)
A laminate for chemical plating was obtained in the same manner as in Example 1, using the TPX) film as a release sheet.

Comparative Example 2 A laminate for chemical plating was obtained in the same manner as in Example 1, using an aluminum foil with a thickness of 50 μm as a gold release sheet.

Comparative Example 3 Melting point: 170°C, thickness: 40 μm Propylene (PP)
A wNA plate for chemical plating was obtained in the same manner as in Example 1 using the film.

Comparative Example 4 A laminate for chemical plating was obtained in the same manner as in Example 1 using an OIJ vinyl fluoride (PVF) film with a melting point of 200° C. and a thickness of 50 μm that had been subjected to matte treatment (surface roughening treatment) on both sides.

Comparative Example 5 A laminate for chemical plating was obtained in the same manner as in Example 6, except that a 50 μm thick aluminum foil was used as the release sheet.

Example 1.2.3.4.5.6 and Comparative Example 1.2.3.
The evaluation results of the heat resistance during the adhesive coating and drying process of the release sheet in 4.5, the releasability of the release sheet as a laminate for chemical plating, and other various requirements are shown in Table 1. It was shi.

One thing that is clear from Table 1 is that according to the present invention, the peel strength of the release sheet can be freely controlled, and the uniform adhesion of the release sheet can be improved.

In addition, it was possible to improve the contamination of the press end plate.

Claims (2)

[Claims] (1) An adhesive layer formed on a release sheet is superimposed on the surface of a plurality of semi-cured thermosetting resin-impregnated base materials,
In a method for producing a chemical plating laminate by heating and pressure molding, the adhesive layer contains partially crosslinked acrylonitrile butadiene rubber and a thermosetting resin, and the release sheet is a plastic with a melting point of 200°C or higher. at least one surface of the film is aluminized,
Alternatively, a method for manufacturing a laminate for chemical plating, characterized by using a composite sheet laminated with aluminum foil having a thickness of 1 to 25 μm. (2) The method for manufacturing a laminate for chemical plating according to claim 1, wherein the adhesive layer contains a phospholipid body.