Electro-deposited copper foil, surface-treated copper foil using the electro-deposited copper foil and copper clad laminate using the surface-treated copper foil, and a method for manufacturing the electro-deposited copper foil

Patent metadata

Field	Value
Publication number	US-9307639-B2
Application number	US-29806807-A
Country	US
Kind code	B2
Filing date	Apr 26, 2007
Priority date	Apr 28, 2006
Publication date	Apr 5, 2016
Grant date	Apr 5, 2016

Abstract

Present invention provides an electro-deposited copper foil having the equivalent low-profile surface as in a conventional low-profile electro-deposited copper foil and extremely large mechanical strength and a method for manufacturing the same. The electro-deposited copper foil is formed by depositing fine copper crystal grains having a small deviation of grain-diameter. The electro-deposited copper foil has a low-profile and glossy surface and has extremely large mechanical strength expressed by a tensile strength as received of 70 kgf/mm 2 to 100 kgf/mm 2 and has a tensile strength after heating (180° C. for 60 minutes) corresponding to 85% or more of the tensile strength as received. The electro-deposited copper foil is manufactured by electrolysis using a sulfuric acid base copper electrolytic solution containing a compound composed of a benzene ring having a sulfo group bonded thereto, a sulfonate of an active sulfur compound and a polymer of a quaternary ammonium salt having a cyclic structure.

First claim

The invention claimed is:

1. An electro-deposited copper foil obtained by electrolysis of a copper electrolytic solution, wherein a tensile strength as received (hereinafter referred to as a “tensile strength as received”) is 88.4 kgf/mm 2 to 100 kgf/mm 2 ,
wherein a tensile strength after heating at 180° C. for 60 minutes (hereinafter referred to as a “tensile strength after heating”) is 85% or more of the tensile strength as received.

2. The electro-deposited copper foil according to claim 1 , wherein a tensile strength as received measured at 30 days after manufacturing is not less than 65 kgf/mm 2 .

3. The electro-deposited copper foil according to claim 1 , wherein an elongation as received (hereinafter referred to as an “elongation as received”) is 3% to 15%.

4. The electro-deposited copper foil according to claim 1 , wherein an elongation after heating at 180° C. for 60 minutes (hereinafter referred to as an “elongation after heating”) is not more than the elongation as received.

5. The electro-deposited copper foil according to claim 1 , wherein a gloss which is measured at a reflection angle of 60° for the transverse direction of a deposit surface (hereinafter referred to as “[Gs(60°)]”), is 80 or more.

6. A surface-treated electro-deposited copper foil characterized in that one, two or more types of treatments selected from a roughening treatment, a rust-proofing treatment and a silane coupling agent treatment are applied to a surface of the electro-deposited copper foil according to claim 1 .

7. A method for manufacturing the electro-deposited copper foil according to claim 1 by electrolysis using a sulfuric acid base copper electrolytic solution, characterized in that the sulfuric acid base copper electrolytic solution contains the following additives A to C:
Additive A: a compound composed of a benzene ring and a heterocyclic ring which contains a nitrogen atom (N) and a bonded mercapto-functional group, or a thiourea-functional compound;
Additive B: a sulfonate of an active sulfur compound;
Additive C: a polymer of a quaternary ammonium salt having a cyclic structure.

8. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the additive A is one, two or more types of compounds selected from an imidazole-functional compound, a thiazole-functional compound, a tetrazole-functional compound and a thiourea-functional compound with an alkane group having 2 or more carbon atoms bonded at both ends.

9. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the additive A has a benzene ring having a sulfo group bonded thereto.

10. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the additive A is one, two or more types of compounds selected from 2-mercapto-5-benzimidazole sulfonic acid, 3(5-mercapto-1H-tetrazolyl)benzene sulfonate, 2-mercaptobenzothiazole or N—N diethylthiourea.

11. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the total concentration of the additive A in the sulfuric acid base copper electrolytic solution is 1 ppm to 50 ppm.

12. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the additive B is 3-mercapto-1-propanesulfonic acid, bis(3-sulfopropyl)disulfide or a mixture thereof.

13. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the concentration of the additive B in the sulfuric acid base copper electrolytic solution is 1 ppm to 80 ppm.

14. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the additive C is a diallyldimethylammonium chloride polymer.

15. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the concentration of the additive C in the sulfuric acid base copper electrolytic solution is 0.5 ppm to 100 ppm.

16. The method for manufacturing an electro-deposited copper foil according to claim 7 , wherein the ratio of the concentration of the additive B to the concentration of the additive C in the sulfuric acid base copper electrolytic solution, that is, a value of [(B concentration)/(C concentration)], is 0.07 to 1.4.

17. The method for manufacturing an electro-deposited copper foil according to claim 6 , wherein the concentration of chlorine in the sulfuric acid base copper electrolytic solution is 5 ppm to 100 ppm.

18. A copper clad laminate obtained by bonding the surface-treated electro-deposited copper foil according to claim 6 to an insulating layer-forming material.

19. A rigid copper clad laminate according to claim 18 , wherein the insulating layer-forming material contains a reinforcement.

20. A rigid printed wiring board comprising the copper clad laminate according to claim 19 .

21. A copper clad laminate according to claim 18 , wherein the insulating layer-forming material is formed of a flexible material having flexibility.

22. A flexible printed wiring board comprising the copper clad laminate according to claim 21 .

23. An electro-deposited copper foil obtained by electrolysis of a copper electrolytic solution, wherein a tensile strength as received (hereinafter referred to as a “tensile strength as received”) is 70 kgf/mm 2 to 100 kgf/mm 2 ,
wherein a tensile strength after heating at 180° C. for 60 minutes (hereinafter referred to as a “tensile strength after heating”) is 85% or more of the tensile strength as received, and
wherein the copper foil has a surface roughness (Rzjis) at a deposit surface of 0.88 micron-meter or less.

24. A surface-treated electro-deposited copper foil characterized in that one, two or more types of treatments selected from a roughening treatment, a rust-proofing treatment and a silane coupling agent treatment are applied to a surface of the electro-deposited copper foil according to claim 23 .

25. A copper clad laminate obtained by bonding the surface-treated electro-deposited copper foil according to claim 24 to an insulating layer-forming material.

26. A copper clad laminate according to claim 25 , wherein the insulating layer-forming material contains a reinforcement.

27. A rigid printed wiring board comprising the copper clad laminate according to claim 26 .

28. A copper clad laminate according to claim 25 , wherein the insulating layer-forming material is formed of a flexible material having flexibility.

29. A flexible printed wiring board comprising the copper clad laminate according to claim 28 .

Assignees

• Sakai Hisao
• Takahashi Masaru
• Matsuda Mitsuyoshi
• Dobashi Makoto
• Mitsui Mining & Smelting Co

Inventors

• Sakai Hisao
• Takahashi Masaru
• Matsuda Mitsuyoshi
• Dobashi Makoto

Classifications

• H05K2201/0397

  Tab · CPC title

• C25D7/0614

  Strips or foils · CPC title

• H05K1/0393

  Flexible materials (H05K1/038 takes precedence; specific organic compositions are classified in H05K1/0313 and subgroups) · CPC title

• C25D1/04 Primary

  Wires; Strips; Foils · CPC title

• Y10T428/12438

  Composite · CPC title