JPS60210449A - Manufacture of laminated board for plating additive - 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 Application Field] The present invention relates to a laminate for additive plating that has 1- good adhesion to copper by chemical copper plating.

[Prior art]

In general, additive plating laminates are substrate materials for manufacturing printed circuit boards using the so-called additive process C2.

In this case, as the insulating adhesive on the surface of the substrate, a composition consisting of acrylonitrile butadiene rubber (hereinafter referred to as NBR) and phenol resin is mainly used. (2) The adhesion between the copper plating film and the adhesive layer is also weak, and the soldering heat resistance required for soldering as a special C2 printed circuit board is poor. It is insufficient.

In order to improve these defects, there are adhesives containing 1m, NHR, phenolic resin, and epoxy resin, but although the solvent resistance is improved, the adhesion between the copper plating film and the adhesive layer is insufficient. .

In addition, NBR, phenolic resin and inorganic compounds 2
- Some adhesives contain adhesives, but in the process of manufacturing laminates for additive plating, the sheets obtained by applying and drying the releasable sort C2 adhesive are placed in a predetermined number of thermosetting sheets with the adhesive side facing inside. Resin-impregnated paper cloth is layered and heated and pressed to integrate to create a double-sided C2 adhesive-attached substrate (in this case, it is extremely difficult to remove the releasable sheet. When C2 is used, it is extremely difficult to peel and remove the adhesive because the adhesive and the metal foil are in close contact with each other.

In addition, due to inappropriate selection of materials for NBR, phenolic resin, and inorganic compounds, copper plating It was not possible to obtain excellent adhesion between the film and the adhesive layer, and good electrical properties were also not obtained.

[Purpose of the invention]

The present invention improves the poor solvent resistance of the adhesive layer and the poor adhesion between the copper plating film and the adhesive layer in the prior art, and enables easy peeling of the release sheet when manufacturing a laminate for additive plating ( It was completed after 17 years of study with the purpose of

The present invention provides an M chest plate for additive plating that has good solvent resistance of the adhesive layer and good adhesion between the copper plating film and the adhesive layer, and can easily (= peel off) one release sheet.

[Structure of the invention]

The present invention is NmL, resol type pheno-I resin.

y)( ・・・・・・・・・(Double soluble decomposition temperature 1!j' 300℃
Sheet C: Coating 41, which has a releasable adhesive consisting of an electrically insulating inorganic compound and a phospholipid body, and this sheet and a desired number of thermosetting resin-impregnated paper cloth are combined with the above-mentioned sheet. Apply the heron agent 41 to the inside 1 and make it 1! This is a method for manufacturing additive plating volume 144#v, which is characterized by kneading, heating and pressurizing and integrating.

As M rubber, a high acrylonitrile-butadiene rubber with a nitrile content of 35% or more is used. The reason for this is that high acrylonitrile-butadiene rubber is good because it can withstand various types of organic abrasions and strong acids and strong alkalis during additive plating processes.

In particular, those with a nitrile content of 35 to 50% are preferred.

The resol type phenolic resin may be a straight type, but oil-modified phenolic resins and alkyl-modified phenolic resins are preferred. The reason for this is that it has good compatibility and reactivity with NBR, and so-called resin vulcanization is possible.

Therefore, it is possible to impart chemical resistance in the additive plating process. Therefore, for such a phenol resin, one molecule of 11N: 94 to 500, and the modification rate (for two, in the case of oily phenol, 10 ~50
%, alkyl StO, is preferred.

The particle size of the ability-like compound is an average particle size of 1frLItfrL~2
0 μm is preferable. In order to strengthen the adhesion between the 5-copper plating film and the adhesive layer after the additive plating process (5 m as primary particles), those having a particle diameter of tm to 5 μm are preferable.

The phospholipid body is used to make it easier to peel off and remove the laminate for additive plating from the adhesion side surface by heating and pressurizing. The addition M is 0.1 to 0.1 to the solid content of the adhesive.
The degree of peeling 1i11+ (fl) can be selected depending on the range of 5%.

The blending ratio of each component is N1 (TL 40-60%, resol type phenolic resin 60-40%, inorganic compound 0.
5-5.0%, phospholipid body 0.1-5.0% is 9L.

Such a formulation may need to be dissolved in a suitable solvent beforehand. Such an adhesive solution is applied to a release sheet.

Metal foil, plastic film, paper, etc. can be used as the release sheet, but metal foil is particularly preferred from the viewpoint of heat resistance during the drying process after applying the adhesive.

Aluminum foil is preferred from the viewpoint of cost.

The drying step is to remove the solvent in the adhesive by drying with hot air (6-) and to advance the thermal reaction between the adhesive component NBR and the phenol resin to a certain extent.

Adhesive application can be carried out using a roll coater, percoater, curtain flow coat, swivel roll, etc. (2) followed by a hot air drying cylinder (2) continuous (drying is possible). The adhesive film thickness is preferably 20 to 200 μm after drying.
Favorable in terms of adhesion and coating work.

The thus obtained adhesive-coated releasable sheet is overlaid with a predetermined number of thermosetting resin-impregnated paper cloth with the adhesive m1 on the inside (2), and is integrated by heating and pressing, followed by additive plating with adhesive. It is possible to make laminates for

The additive process will be briefly explained below.

The releasable sheet is peeled off and removed from the laminate for additive plating. After drilling and drying as required (1), oxidize and roughen the adhesive layer with chromic acid/sulfuric acid, perform activation treatment for copper plating with baladium, etc., and apply plating resist as necessary. 1y, chemical copper plating (2) can form a conductor circuit. History (-1 required 1: If required, electrolytic copper plating can also be used. After that, the plating resist must be removed according to "U+: You may.

〔Effect of the invention〕

The laminate for additive plating obtained by the present invention has the following features.

1. Because the adhesive contains fine particles of inorganic compounds, oxidation and surface roughening caused by chromic acid/sulfuric acid
: Can form a fine rough surface.

2. Therefore, chemical copper plating (2) has extremely good adhesion and deposition speed, and there is no peeling or blistering of the circuit during soldering after circuit formation.

5 Appropriate proportion of NBR and resol type phenolic resin 1
: A three-dimensional network structure is formed.

Furthermore, due to the reinforcing effect of the inorganic compound, the adhesive layer does not swell, dissolve, peel, deteriorate, etc. in contrast to various organic solvent treatments in the plating resist forming step C:.

4. The removable sheet can be easily removed without impairing the above-mentioned features.

〔Example〕

The method for producing a laminate for additive plating according to the present invention will be described below (= Examples).

Example I NIJR (containing 37% acrylonitrile) 10001
00O, (average particle size 15 mμm) 20 ν ten 2 methyl ether ketone 5000 The above resin mixture was stirred and mixed at 80° C. for 3 hours to obtain an adhesive solution.

This adhesive solution was applied to a 50 μm thick aluminum foil (using a two-roll coating method and dried through a continuous drying cylinder at 50 to 160° C.). The adhesive film thickness was 100 μm.

Lay this adhesive-coated aluminum foil on each side of 8 pieces of epoxy resin-impregnated glass cloth with the adhesive side on the inside.
The product was heated and pressed for 20 minutes to obtain a laminate for additive plating with a thickness of 1.6 mm and an adhesive on both sides.

Example 2 NBR (Ac90 nitrile content 35%) 1000.
9 Resol type phenolic resin 1200 Tie, (average particle size 0.3 μm) 15 Lenthene 3 Toluene 2000 Methyl ether ketone 3000 The above resin mixture was stirred at 80°C for 3 hours and combined with O.
...A glue solution was obtained.

This adhesive solution was applied to a 100 μm thick polypropylene sheet (transfer coated using a Nyquiz roll method and heated to 50 to 130°C.
It was dried through a continuous drying cylinder. Adhesive film thickness is 50μm
It's true.

Thereafter, heating and pressing were carried out in the same manner as in Example 1 to obtain a laminate for additive plating.

Comparative example I NBR (acrylonitrile content 35%) 100ON
lO- Novolak type alkyl modified phenol resin 1000#
Lecithin 2 Methyl ethyl ketone 5000 The resin mixture described in E was stirred and mixed at 80° C. for 3 hours to obtain an adhesive solution. This adhesive solution was applied to a 50 μm thick aluminum foil and dried. The adhesive film thickness was 50 μm.

Hereinafter, a laminate for additive plating was obtained in the same manner as in Example 1.

Comparative example 2 NBR, (acrylonitrile content 20%) 1ooo
11 Novolak-type Kannie-modified phenolic resin 100
0 StO, (average particle size 40 mμm) 5 Methyl ethyl ketone 5000 The above resin mixture was stirred and mixed at 80° C. for 3 hours to obtain an adhesive solution. The adhesive solution was applied to a 50 μm thick aluminum foil and dried. The adhesive film thickness was 100 μm.

Thereafter, C2 was carried out in the same manner as in Example 1 to obtain a laminate for additive plating.

Mr@My for additive plating obtained in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 was subjected to the following Tal~(g
) was processed and chemically plated with copper.

The results of evaluating the characteristics are shown in Table 1.

<Chemical copper plating process> (a) Removal of peelable sheet (b) Chromic acid/sulfuric acid mixture treatment (C) Activation treatment (d) Plating resist formation (e) Chemical copper plating (Plating 1% I 39 μm
) (f) Removal of plating resist (g) Drying 1st The test method for peeling strength and soldering heat resistance with surface shrinkage is in accordance with JIS C6481.

Patent applicant: Sumitomo Bakelite Co., Ltd. 13-

Claims (1)

[Scope of Claims] 1. Acrylonitrile-butadiene rubber containing 35% or more of acrylonitrile-containing phase, resol type fair resin, --- O... (= insoluble and decomposition temperature 30
Adhesive material 1 consisting of an electrically insulating inorganic compound and a phospholipid substance at a temperature of 0°C or higher is coated on a releasable sheet and dried, and this sheet and an arbitrary number of thermosetting resin-impregnated paper cloth are bonded together as described above. A method for producing a laminate for additive plating, characterized in that the adhesive-coated surfaces of the sheets are placed on the inside C2, and the sheets are stacked and integrated under heat and pressure. 2. The adhesive film thickness after drying is 20 μffl to 200 μm. A method for manufacturing a laminate for additive plating according to claim 1, characterized in that: