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Copper foil with primer resin layer and laminate using the same

A technology of resin layer and primer, which is applied in the direction of synthetic resin layered products, primer, coating, etc., can solve the corrosion and oxidation of copper foil surface, the inability to improve the bonding strength, and the inability to improve the heat resistance and mechanical strength of the bonding strength. Satisfactory, etc., to achieve improved performance, reduced total etching costs, and no hardening shrinkage

Inactive Publication Date: 2009-06-10
NIPPON KAYAKU CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, since the surface of the copper foil is usually coated with an amine compound, a long-chain alkyl compound, or a siloxane compound as a surface treatment agent such as a rust inhibitor, the polyimide precursor is directly coated with a casting method. In the two-layer CCL obtained by using the above-mentioned materials, the bonding strength between the copper foil and the polyimide resin substrate cannot be improved as in the above-mentioned case where the substrate resin is bonded by pressure.
In addition, when the surface treatment agent is removed through a degreasing process or a cumbersome process called soft etching, the surface of the copper foil is exposed to the atmosphere or the polyimide precursor to cause corrosion and oxidation.
In addition, untreated copper foil that has not been subjected to surface treatment such as roughening treatment or anti-rust treatment has problems with adhesive strength
In order to solve this problem, although there is an example of using a soluble polyimide resin with high adhesive strength to a copper foil with a small uneven shape (Patent Document 5), its adhesive strength and heat resistance when it is made into a substrate and mechanical strength are still unsatisfactory

Method used

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  • Copper foil with primer resin layer and laminate using the same
  • Copper foil with primer resin layer and laminate using the same
  • Copper foil with primer resin layer and laminate using the same

Examples

Experimental program
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Effect test

Embodiment

[0059] The present invention will be described more specifically by way of examples below, but the present invention is not limited to these examples.

[0060] The method of measuring the change of the surface of the copper foil in the copper foil with a primer resin layer and the adhesive strength of the copper clad laminate is as follows.

[0061] 1. Changes on the surface of copper foil

[0062] Regarding the change of the copper foil surface in the primer resin layer copper foil, the state of the copper foil surface immediately after forming the primer resin layer and the change of the copper foil surface one week later were visually observed.

[0063] 2. Adhesion strength between primer resin layer and copper foil in copper clad laminates

[0064] A 10 mm wide pattern was masked on the copper foil side of the copper clad laminate obtained in the example, and the copper foil except the masked part was dissolved to form a 10 mm wide copper foil pattern. Use an adhesive sh...

Synthetic example 1

[0066] In a 300ml reactor equipped with a thermometer, reflux condenser, Dean-Stark device, powder inlet, nitrogen introduction device and stirring device, add 1,3-bis-(3-aminophenoxy)benzene as a diamine component (APB-N, manufactured by Mitsui Chemicals Co., Ltd., molecular weight 292.34, hereinafter only referred to as APB-N) 24.84g (0.085 moles), while feeding dry nitrogen, add 38.42g of methyl benzoate as a solvent, and at 60 °C and stirred for 30 minutes. Then, 26.88 g (0.087 mol) of 4,4'-oxydiphthalic anhydride (ODPA, manufactured by MANAC, molecular weight 310.22, hereinafter simply referred to as ODPA) as a tetracarboxylic dianhydride component was added as a solvent 57.63 g of γ-butyrolactone, 0.868 g of γ-valerolactone as a catalyst, 1.371 g of pyridine, and 22.2 g of toluene as a dehydrating agent. The inside of the reactor was heated to 180° C., and the heating ring closure reaction was performed for 6 hours while removing water generated in the fractionation tub...

Synthetic example 2

[0071]In a 500ml reactor equipped with a thermometer, reflux condenser, Dean-Stark device, powder inlet, nitrogen inlet and stirring device, add 1,3-bis-(3-aminophenoxy)benzene as a diamine component (APB-N) 14.67 g (0.050 mol), 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone (ABPS, manufactured by Nippon Kayaku Co., Ltd., molecular weight 280.3) 26.13 g (0.093 mol) , while blowing dry nitrogen gas, 64.02 g of methyl benzoate was added as a solvent, and stirred at 60° C. for 30 minutes. Then, 45.38 g (0.146 mol) of 4,4'-oxydiphthalic anhydride (ODPA) as a tetracarboxylic dianhydride component, 96.03 g of γ-butyrolactone as a solvent, and γ-butyrolactone as a catalyst were added thereto. - 1.465 g of valerolactone, 2.314 g of pyridine, and 32.5 g of toluene as a dehydrating agent. The inside of the reactor was heated to 180° C., and the heating ring closure reaction was performed for 6 hours while removing water generated in the fractionation tube. After the imidization reaction ...

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Abstract

Disclosed is a copper foil having a primer resin layer for increasing the adhesion strength between a substrate resin and a copper foil surface which is not subjected to a roughening treatment.Also disclosed is a laminate using such a copper foil. Specifically disclosed are a copper foil and laminate having a primer polyimide layer which is characterized by using a polyimide represented by the formula (1) below as a primer resin. (1) (In the formula, R1 represents a tetravalent aromatic group which is a residue of a dicarboxylic acid dianhydride component (pyromellitic anhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride or 2,3,6,7-naphthalenetetracarboxylic acid dianhydride); R2 represents a divalent aromatic group which is a residue of a diamine component (1,3-bis-(3-aminophenoxy)benzene, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone or / and 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane); and n1 represents the number of repetition). The copper foil and laminate have high adhesion strength, and are thus suitably used for flexible printed wiring boards.

Description

technical field [0001] The present invention relates to a primer resin, a copper foil with the primer resin layer and its manufacturing method, and a laminate using the copper foil. In the present invention, the copper foil does not need to be roughened, and the Copper foil made by thinly coating solvent-soluble polyimide resin on the surface of copper foil and drying it can ensure good adhesion between copper foil and resin substrates for flexible printed wiring boards such as polyimide film substrates . Background technique [0002] Usually, polyimide film is laminated with metal foil (mainly copper foil) as a single-sided or double-sided flexible copper-clad laminate, or as a flexible printed wiring board or multilayer printed wiring board. use. Among them, in the copper-clad laminate called 2-layer CCL (Copper clad laminate), the polyimide film and the copper foil are bonded directly without passing through the adhesive layer. It is very useful from the viewpoint of t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G73/10B32B15/088C09D5/00C09D179/08H05K3/38
CPCB32B27/34H05K1/0393C09D5/002C08G73/1082C08G73/1064H05K2201/0358H05K3/386B32B15/08C09D179/08C08G73/1067C08G73/1046H05K2201/0154C09J179/08C08G73/10B32B15/20B32B27/281B32B2255/06B32B2255/205B32B2255/26B32B2307/306B32B2307/538B32B2307/546B32B2457/08Y10T428/2804B32B15/088
Inventor 内田诚田中龙太朗林本成生茂木繁西头光代
Owner NIPPON KAYAKU CO LTD
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