Epoxy resin composition, and adhesive film and prepreg using the composition, and multilayer printed-wiring board using them, and process for manufacturing the same

• US 6,403,221 B1
• Filed: 10/11/2000
• Issued: 06/11/2002
• Est. Priority Date: 10/13/1999
• Status: Expired due to Term

• Current Assignee: Ajinomoto Co., Inc.
• Original Assignee: Ajinomoto Co., Inc.
• Inventors: Nakamura, Shigeo, Yokota, Tadahiko
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): Feely, Michael J
• Application Number:
  US09/684,671
• Time in Patent Office: 608 Days
• Field of Search: 428/413, 428/418, 428/414, 428/901, 428/297.4, 523/427, 523/428, 523/429, 427/96, 427/307, 427/386
• US Class Current: 428/416
• CPC Class Codes: C08G 59/621 Phenols
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 71/00 Compositions of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: H01L 23/49894 Materials of the insulating layers or coatings
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: H05K 3/4661 Adding a circuit layer by direct wet plating, e.g. electroless plating; insulating materials adapted therefor other insulating materials H05K3/387
• CPC Class Codes: Y10S 428/901 Printed circuit
• CPC Class Codes: Y10T 428/24994 Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/249941 Fiber is on the surface of a polymeric matrix having no embedded portion
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/287 including epoxy group or epoxy polymer
• CPC Class Codes: Y10T 428/2971 Impregnation
• CPC Class Codes: Y10T 428/31511 Of epoxy ether
• CPC Class Codes: Y10T 428/31515 As intermediate layer
• CPC Class Codes: Y10T 428/31522 Next to metal
• CPC Class Codes: Y10T 428/31529 Next to metal

Abstract

Epoxy resin compositions which comprise, as essential components, (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a phenolic curing agent, (C) a phenoxy resin containing a bisphenol S skeleton and having a weight average molecular weight of 5,000 to 100,000, and (D) a curing accelerator, are useful for making adhesive films formed by coating the epoxy resin composition on a supporting base film. Such compositions are also useful for making prepregs, by coating and/or impregnating a sheet-shaped reinforced base material made of a fiber with the resin composition, as well as multilayer printed-wiring boards made with such prepregs. Such epoxy resin compositions are also useful for forming conductor layers with excellent adhesiveness without requiring, in the insulating layer, a roughening component which deteriorates performance, as well as multilayer printed-wiring boards.

Claims

1. An epoxy resin composition comprising, as the essential components, (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a phenolic curing agent, (C) a phenoxy resin containing a bisphenol S skeleton and having a weight average molecular weight of 5,000 to 100,000, and (D) a curing accelerator, wherein the epoxy resin (A) contains a phosphorus atom.

2. The epoxy resin composition according to claim 1, wherein said phenolic curing agent (B) contains a nitrogen atom.

3. The epoxy resin composition according to claim 1, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

4. The epoxy resin composition according to claim 1, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

5. An adhesive film which is obtainable by forming a thin film of an epoxy resin composition according to claim 1 on a supporting base film.

6. A multilayer printed-wiring board which is obtainable by the steps of (a) laminating the adhesive film according to claim 5 on a patterned internal-layer circuit board under conditions of pressurizing and heating, (b) detaching the supporting base film, if necessary, (c) curing the epoxy resin composition under heating, (d) roughening the surface of the cured product with an oxidizing agent, and (e) forming a conductor layer on the roughened surface by plating.

7. The multilayer printed-wiring board according to claim 6, wherein said phenolic curing agent (B) contains a nitrogen atom.

8. The multilayer printed-wiring board according to claim 6, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

9. The multilayer printed-wiring board according to claim 6, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

10. A process for manufacturing a multilayer printed-wiring board comprising the steps of (a) laminating the adhesive film according to claim 5 on a patterned internal-layer circuit board under conditions of pressurizing and heating, (b) detaching the supporting base film, if necessary, (c) curing the epoxy resin composition under heating, (d) roughening the surface of the cured product with an oxidizing agent, and (e) forming a conductor layer on the roughened surface by plating.

11. The process according to claim 10, wherein said phenolic curing agent (B) contains a nitrogen atom.

12. The process according to claim 10, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

13. The process according to claim 10, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

14. A laminate which is obtainable by the steps of (a) laminating the adhesive film according to claim 5 on an etched copper surface of a copper foil-clad laminate under conditions of pressurizing and heating, wherein said copper foil-clad laminate comprises at least one copper foil-clad surface;

(b) detaching the supporting base film, if necessary, and (c) curing the adhesive film with heating.

15. The laminate according to claim 14, wherein said phenolic curing agent (B) contains a nitrogen atom.

16. The laminate according to claim 14, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

17. The laminate according to claim 14, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

18. The adhesive film according to claim 5, wherein said phenolic curing agent (B) contains a nitrogen atom.

19. The adhesive film according to claim 5, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

20. The adhesive film according to claim 5, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

21. A prepreg which is obtainable by coating and/or impregnating a sheet-shape reinforced base material made of a fiber with an epoxy resin composition according to claim 1.

22. A multilayer printed-wiring board which is obtainable by the steps of (a) laminating the prepreg according to claim 21 on a patterned internal-layer circuit board under conditions of pressurizing and heating to integrate them, (b) roughening the surface of the prepreg with an oxidizing agent, and (c) forming a conductor layer on the roughened surface by plating.

23. The multilayer printed-wiring board according to claim 22, wherein said phenolic curing agent (B) contains a nitrogen atom.

24. The multilayer printed-wiring board according to claim 22, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

25. The multilayer printed-wiring board according to claim 22, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

26. A process for manufacturing a multilayer printed-wiring board comprising the steps of (a) laminating the prepreg according to claim 21 on a patterned internal-layer circuit board under conditions of pressurizing and heating to integrate them, (b) roughening a surface of the prepreg with an oxidizing agent, and (c) forming a conductor layer on the roughened surface by plating.

27. The process according to claim 26, wherein said phenolic curing agent (B) contains a nitrogen atom.

28. The process according to claim 26, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

29. The process according to claim 26, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

30. A laminate which is obtainable by laminating the prepreg according to claim 21 on an etched copper surface of a copper foil-clad laminate under conditions of pressurizing and heating, wherein said copper foil-clad laminate comprises at least one copper foil-clad surface.

31. The laminate according to claim 30, wherein said phenolic curing agent (B) contains a nitrogen atom.

32. The laminate according to claim 30, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

33. The laminate according to claim 30, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

34. A laminate which is obtainable by laminating the prepreg according to claim 21 on a surface of a substrate under conditions of pressurizing and heating.

35. The laminate according to claim 34, wherein said phenolic curing agent (B) contains a nitrogen atom.

36. The laminate according to claim 34, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

37. The laminate according to claim 34, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

38. The prepreg according to claim 21, wherein said phenolic curing agent (B) contains a nitrogen atom.

39. The prepreg according to claim 21, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

40. The prepreg according to claim 21, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

41. A multilayer printed-wiring board comprising a cured product of an epoxy resin composition according to claim 1, wherein said cured product comprises a roughened surface having a plated conductor layer formed thereon, and wherein said cured product comprises a second surface closely laminated onto a patterned internal-layer circuit board.

42. The multilayer printed-wiring board according to claim 41, wherein said phenolic curing agent (B) contains a nitrogen atom.

43. The multilayer printed-wiring board according to claim 41, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

44. The multilayer printed-wiring board according to claim 41, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

45. A multilayer printed-wiring board which is obtainable by the steps of (a) coating a patterned internal-layer circuit board with an epoxy resin composition according to claim 1, (b) curing it under heating, (c) roughening the surface of the cured product with an oxidizing agent, and (d) forming a conductor layer on the roughened surface by plating.

46. The multilayer printed-wiring board according to claim 45, wherein said phenolic curing agent (B) contains a nitrogen atom.

47. The multilayer printed-wiring board according to claim 45, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

48. The multilayer printed-wiring board according to claim 45, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

49. A process for manufacturing a multilayer printed-wiring board comprising the steps of (a) coating a patterned internal-layer circuit board with an epoxy resin composition according to claim 1, (b) curing said composition with heating to obtain a cured composition, (c) roughening the surface of said cured composition with an oxidizing agent to obtain a roughened surface, and (d) forming a conductor layer on said roughened surface by plating.

50. The process according to claim 49, wherein said phenolic curing agent (B) contains a nitrogen atom.

51. The process according to claim 49, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

52. The process according to claim 49, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).

53. A laminate which is obtainable by the steps of (a) coating an etched copper surface of a copper foil-clad laminate with an epoxy resin composition according to claim 1, wherein said copper foil-clad laminate comprises at least one copper foil-clad surface;

and (b) curing said composition with heating.

54. The laminate according to claim 53, wherein said phenolic curing agent (B) contains a nitrogen atom.

55. The laminate according to claim 53, wherein said phenoxy resin (C) contains a bisphenol S skeleton and a biphenyl skeleton, and has a weight average molecular weight of 5,000 to 100,000.

56. The laminate according to claim 53, wherein 5 to 50 parts by weight of said phenoxy resin (C) and 0.05 to 10 parts by weight of said curing accelerator (D) are mixed with 100 parts by weight in total of said epoxy resin (A) and said phenolic curing agent (B).