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Resin composite electrolytic copper foil, copper clad laminate and printed wiring board

a technology of copper clad laminate and printed wiring board, which is applied in the directions of printed circuit aspects, transportation and packaging, chemistry apparatus and processes, etc., can solve the problems of lack of adhesion strength, heat resistance, adhesiveness and heat resistance, and deterioration of location accuracy of circuit and adhesion strength, so as to improve heat resistance and improve plate adhesion strength.

Inactive Publication Date: 2012-07-26
MITSUBISHI GAS CHEM CO INC +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0009]The subject of the invention is to provide a copper clad laminate, a printed wiring board and a resin composite copper foil for use in producing the printed wiring board, to provide a resin composite electrolytic copper foil having further improved heat resistance and improved plate adhesion strength when plated after desmear treatment in the work process of an additive method, and to further allow formation of a fine circuit of a printed wiring board by using the resin composite electrolytic copper foil.
[0027]A resin composite electrolytic copper foil obtained in the invention can, since the adhesion strength of a copper clad laminate to a resin composition is excellent, have an electrolytic copper foil with small unevenness on a copper foil matt surface, roughened by attaching roughening particles, applied, and by using this resin composite electrolytic copper foil, a copper clad laminate with good economic efficiency and heat resistance under moisture absorption can be obtained. Since this copper clad laminate can be preferably used as a high density printed wiring board with a fine circuit, is particularly excellent in the adhesion strength of plated copper after desmear treatment and have further improved heat resistance, industrial practicality of the resin composite electrolytic copper foil of the invention is extremely high.

Problems solved by technology

Although these electrolytic copper foils have good adhesion strength, there are problems such that when forming a fine circuit by an etching method, a part of a convex portion of the copper foil is liable to remain on an insulating resin surface due to influence of the unevenness on the copper foil matt surface, that as the etching time is extended in order to completely remove this, the circuit is over-etched, deteriorating location accuracy of the circuit and adhesion strength, and the like.
However, when this copper foil is applied to a copper clad laminate with a highly heat resistant thermosetting resin and the like having essentially weak adhesion strength, lack of adhesion strength becomes a problem in a fine circuit, which has been an obstacle to ultrathinning.
However, these resin composite copper foils and copper clad laminates using a copper foil having a semi-set resin film bonded have problems in heat resistance, adhesiveness and heat resistance under moisture absorption, and have required further improvement.
However, in a laminate having this surface treated copper foil laminated with an insulating heat resistant thermosetting resin, a fine circuit by an additive method could not be applied to a high density printed wiring board due to the problem of lacking the adhesion strength of plated copper.
Moreover, although a resin composite electrolytic copper foil having a resin composition layer (B) comprising a block copolymerized polyimide resin (a) and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane (b) formed (Japanese Patent Application Laid-open Publication No. 2008-254352) has been suggested in order to solve this problem, when desmear treatment is conducted in the work process of the additive method, the plate adhesion strength was insufficient.

Method used

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  • Resin composite electrolytic copper foil, copper clad laminate and printed wiring board
  • Resin composite electrolytic copper foil, copper clad laminate and printed wiring board
  • Resin composite electrolytic copper foil, copper clad laminate and printed wiring board

Examples

Experimental program
Comparison scheme
Effect test

synthesis example 1

[0083]To a 2 L three neck flask having a reflux cooler equipped with a ball cooling tube mounted on a trap with an anchor shaped stirring stick, a nitrogen introducing tube and a stop cock of stainless steel, 117.68 g (400 mmol) of 3,4,3′,4′-biphenyl tetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis(3-aminophenoxy)benzene, 4.0 g (40 mmol) of γ-valerolactone, 4.8 g (60 mmol) of pyridine, 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were added, heated at 180° C. for 1 hour and then cooled to about room temperature, and subsequently 29.42 g (100 mmol) of 3,4,3′,4′-biphenyl tetracarboxylic dianhydride, 82.12 g (200 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 200 g of NMP and 40 g of toluene were added, mixed at room temperature for 1 hour and then heated at 180° C. for 3 hours to obtain a block copolymerized polyimide resin with a solid content of 38%. In this block copolymerized polyimide resin, general formula (1): general formula...

synthesis example 2

[0084]To a 2 L three neck flask having a reflux cooler equipped with a ball cooling tube mounted on a trap with an anchor shaped stirring stick, a nitrogen introducing tube and a stop cock of stainless steel, 117.68 g (400 mmol) of 3,4,3′,4′-biphenyl tetracarboxylic dianhydride, 123.18 g (300 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4.0 g (40 mmol) of γ-valerolactone, 4.8 g (60 mmol) of pyridine, 300 g of NMP and 20 g of toluene were added, heated at 180° C. for 1 hour and then cooled to about room temperature, and subsequently 29.42 g (100 mmol) of 3,4,3′,4′-biphenyl tetracarboxylic dianhydride, 58.47 g (200 mmol) of 1,3-bis(3-aminophenoxy)benzene, 200 g of NMP and 40 g of toluene were added, mixed at room temperature for 1 hour and then heated at 180° C. for 3 hours to obtain a block copolymerized polyimide resin with a solid content of 38%. In this block copolymerized polyimide resin, general formula (1): general formula (2)=2:3, number average molecular weight: 75000, ...

synthesis example 3

[0085]To a 2 L three neck flask having a reflux cooler equipped with a ball cooling tube mounted on a trap with an anchor shaped stirring stick, a nitrogen introducing tube and a stopcock of stainless steel, 117.68 g (400 mmol) of 3,4,3′,4′-biphenyl tetracarboxylic dianhydride, 73.08 g (250 mmol) of 1,3-bis(3-aminophenoxy)benzene, 4.0 g (40 mmol) of γ-valerolactone, 4.8 g (60 mmol) of pyridine, 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were added, heated at 180° C. for 1 hour and then cooled to about room temperature, and subsequently 29.42 g (100 mmol) of 3,4,3′,4′-biphenyl tetracarboxylic dianhydride, 102.65 g (250 mmol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 200 g of NMP and 40 g of toluene were added, mixed at room temperature for 1 hour and then heated at 180° C. for 2 hours to obtain a block copolymerized polyimide with a solid content of 38%. In this block copolymerized polyimide, general formula (1): general formula (2)=1:1, n...

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Abstract

The problem of the invention is to provide a resin composite electrolytic copper foil having further improved heat resistance and improved plate adhesion strength when plated after desmear treatment in the work process of an additive method. The solution is to form a roughened surface having a plurality of minute projections, a surface roughness (Rz) within a range of 1.0 μm to 3.0 μm and a lightness value of not more than 30 on one surface of an electrolytic copper foil, and form a layer of a resin composition containing a block copolymerized polyimide resin having a structure that imide oligomers of a first structural unit and a second structural unit are bonded alternately and repeatedly on the roughened surface.

Description

BACKGROUND OF THE INVENTION[0001]1. Field of the Invention[0002]This invention relates to a resin composite electrolytic copper foil used in producing a printed wiring board, a copper clad laminate having the resin composite electrolytic copper foil and a B-stage resin composition layer laminate molded, a printed wiring board using the copper clad laminate, and a method for producing the printed wiring board. More specifically, it relates to a resin composite electrolytic copper foil having a copper foil with very small unevenness on a copper foil matt surface applied and being excellent in adhesion strength to a resin composition, a copper clad laminate using the resin composite electrolytic copper foil and having good heat resistance, and a high density printed wiring board using the copper clad laminate and capable of forming a fine circuit.[0003]2. Description of the Related Art[0004]In recent years, in order to mount an electronic component such as a semiconductor part for use ...

Claims

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Application Information

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IPC IPC(8): B32B15/08
CPCB32B15/08C25D1/04C25D7/0614H05K1/0346C25D5/022H05K2201/0154H05K2201/0355H05K2201/0358H05K2203/0307H05K3/384Y10T428/31681C25D7/0678H05K1/0373H05K1/09H05K3/4652
Inventor NOZAKI, MITSURUNOMOTO, AKIHIROAKIYAMA, NORIKATSUNAGATA, EIJIYANO, MASASHI
Owner MITSUBISHI GAS CHEM CO INC
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