Thermally stable adhesive

• US 4,604,230 A
• Filed: 10/15/1984
• Issued: 08/05/1986
• Est. Priority Date: 10/15/1984
• Status: Expired due to Fees

• Current Assignee: National Starch And Chemical Corporation (Ingredion Incorporated)
• Original Assignee: Stauffer Chemical Company (Nouryon BV)
• Inventors: Goswami, Jagadish C., Aurichio, Joseph A., Zingaro, Joseph R.
• Primary Examiner(s): Pertilla, Theodore E.
• Application Number:
  US06/660,593
• Time in Patent Office: 659 Days
• Field of Search: 525/112, 525/423, 252/512, 252/514, 523/400, 523/443, 523/444, 523/458, 524/439, 524/440
• US Class Current: 252/514
• CPC Class Codes: C08F 283/00 Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C09J 163/00 Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• CPC Class Codes: C09J 179/00 Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00

Abstract

A novel adhesive exhibiting low outgassing upon exposure to high temperature is disclosed. The instant adhesive comprises: (a) a soluble polyimide resin, (b) a solvent for said polyimide resin, (c) a tackifier, (d) an epoxy resin, (e) a hardener for said epoxy resin, (f) a catalyst which catalyzes the reaction between the epoxy and hardener, (g) a cross-linking agent reactive with the polyimide solvent of (b), (h) a catalyst which accelerates the reaction between (b) and (g), and (i) a filler material. Optionally, the adhesive may also contain a conductive material. A process for making the adhesive is also disclosed.

Claims

1. An adhesive composition comprising:

(a) a soluble polyimide resin;

(b) an appropriate solvent for said polyimide resin;

(c) a tackifier;

(d) an epoxy resin;

(e) a hardener for said epoxy resin;

(f) a catalyst which accelerates the curing of said epoxy resin;

(g) a cross-linking agent reactive with the polyimide solvent of (b);

(h) a catalyst which catalyzes the cross-linking reaction of (b) and (g); and

(i) a filler material.

2. A composition according to claim 1 wherein the soluble polyimide resin is a polyimide resin derived from phenylindane diamines and dianhydrides, polyamide acid or a partially imidized polyamide acid.

3. A composition according to claim 1 wherein said soluble polyimide resin comprises from about 1.5% to about 21% by weight of the reaction mixture.

4. A composition according to claim 1 wherein the polyimide solvent is an ethylenically unsaturated organic compound having one or more unsaturated sites.

5. A composition according to claim 4 wherein said polyimide solvent is N-vinyl pyrrolidinone.

6. A composition according to claim 1 wherein said polyimide solvent comprises from about 15% to about 60% by weight of the adhesive composition.

7. A composition according to claim 1 wherein said tackifier is selected from the group of conventional tackifiers.

8. A composition according to claim 7 wherein said tackifier is polyvinyl pyrrolidinone.

9. A composition according to claim 1 wherein said tackifier comprises from about 0.3% to about 3% by weight of the adhesive composition.

10. A composition according to claim 1 wherein said epoxy resin is a glycidyl polyether of a polyhydric phenol.

11. A composition according to claim 1 wherein said epoxy resin is a glycidyl ether of a polyhydric alcohol.

12. A composition according to claim 1 wherein said epoxy resin is a glycidyl ester of a polycarboxylic acid.

13. A composition according to claim 1 wherein said epoxy resin is a glycidyl polyether of a polyhydric alchohol.

14. A composition according to claim 1 wherein said epoxy resin comprises from but 3% to abot 30% by weight of the adhesive composition.

15. A composition according to claim 1 wherein said hardener for said epoxy resin is an aliphatic amine having at least three active amine hydrogen atoms per molecule.

16. A composition according to claim 1 wherein said hardener for said epoxy resin is an amidoamine obtained by reacting a polyamine with a fatty acid.

17. A composition according to claim 1 wherein said hardener for said epoxy resin is selected from the group consisting of mercaptans and isocyanates.

18. A composition according to claim 1 wherein said hardener for said epoxy resin is an anhydride curing agent.

19. A composition according to claim 18 wherein said hardeners for said epoxy resin are methyl-bicyclo (2.2.1)heptane-2,3 dicarboxylic anhydride isomers.

20. A composition according to claim 1 wherein said hardener for said epoxy resin is an aromatic amine.

21. A composition according to claim 1 wherein said hardener for said epoxy resin comprises from about 3% to about 15% by weight of the adhesive composition.

22. A composition according to claim 1 wherein said catalyst accelerating the curing of said epoxy resin is an alkyl or aryl substituted imidazole catalyst.

23. A composition according to claim 22 wherein said catalyst is 2-ethyl, 2-methyl imidazole.

24. A composition according to claim 1 wherein said catalyst comprises from about 0.3% to about 3% by weight of the adhesive composition.

25. A composition according to claim 1 wherein said cross-linking agent reactive with the polyimide solvent is a polyethylenically unsaturated organic compound.

26. A composition according to claim 25 wherein said cross-linking agent is triallyl-S-triazine-2,4,6 trione.

27. A composition according to claim 2 wherein said cross-linking agent comprises from about 15% to about 60% by weight of the adhesive composition.

28. A composition according to claim 1 wherein said catalyst catalyzing the cross-linking reaction of (b) and (g) is an organic catalyst having a half life of the same order as the cure time at the temperature chosen.

29. A composition according to claim 28 wherein said organic catalyst is an organic peroxide.

30. A composition according to claim 29 wherein said organic peroxide is di-tertiary butyl peroxide.

31. A composition according to claim 28 wherein said organic catalyst is a peroxyketal.

32. A composition according to claim 29 wherein said organic catalyst is a t-amyl peroxide.

33. A composition according to claim 1 wherein said catalyst catalyzing the cross-linking reaction between (b) and (g) is 1,1'"'"'-azobis(cyclohexanecarbonitrile).

34. A composition according to claim 1 wherein said catalyst catalyzing the cross-linking reaction between (b) and (g) comprises from about 1.5% to abut 15% by weight of the adhesive composition.

35. A composition according to claim 1 wherein said filler material comprises glass or silica fillers.

36. A composition according to claim 35 wherein said filler is glass.

37. A composition according to claim 36 wherein said filler material comprises glass fillers of a size less than 10 microns and preferably of a melting point from about 350°

C. to about 500°

C.

38. A composition according to claim 35 wherein said filler is silica.

39. A composition according to claim 38 wherein said filler is silica of a size less than 1 micron.

40. A composition according to claim 1 wherein said filler material comprises from about 0.3% to about 15% by weight of the adhesive composition.

41. A composition according to claim 1, further comprising a conductive material.

42. A composition according to claim 41 wherein the conductive material is a noble metal.

43. A composition according to claim 42 wherein the noble metal is silver.

44. A composition according to claim 42 wherein the conductive material is a noble metal coated on a non-noble metal.

45. A composition according to claim 41 wherein the conductive material comprises from about 55% to about 70% by weight of the reaction mixture.

46. A process for the manufacture of an adhesive composition comprising:

(a) mixing together the polyimide resin and the polyimide solvent,

(b) adding the tackifier which imparts tackiness to the B-staged adhesive film,

(c) mixing together the epoxy and curing agent for the epoxy and then adding this mixture to (b),

(d) adding a catalyst dissolved in the polyimide solvent to mixture (c),

(e) mixing together the second cross-linking agent and a catalyst which catalyzes the cross-linking reaction between the cross-linking agent and the polyimide solvent and adding this mixture to the mixture of (d), and

(f) adding a suitable amount of filler.

47. A process according to claim 46 wherein the soluble polyimide resin is a polyimide resin derived from phenylindane diamines and dianhydrides, polyamide acid or a partially imidized polyamide acid.

48. A process according to claim 46 wherein said soluble polyimide resin comprises from about 1.5% to about 21% by weight of the reaction mixture.

49. A process according to claim 46 wherein the polyimide solvent is an ethylenically unsaturated organic compound having one or more unsaturated sites.

50. A process according to claim 46 wherein said polyimide solvent comprises from about 15% to about 60% by weight of the adhesive composition.

51. A process according to claim 46 wherein said tackifier is selected from the group of conventional tackifiers.

52. A process according to claim 46 wherein said tackifier comprises from about 0.3% to about 3% by weight of the adhesive composition.

53. A process according to claim 46 wherein said epoxy resin is a glycidyl polyether of a polyhydric phenol.

54. A process according to claim 46 wherein said epoxy resin is a glycidyl ether of a polyhydric alcohol.

55. A process according to claim 46 wherein said epoxy resin is a glycidyl ester of a polycarboxylic acid.

56. A process according to claim 46 wherein said epoxy resin is a glycidyl polyether of a polyhydric alcohol.

57. A process according to claim 46 wherein said epoxy resin comprises from about 3% to about 30% by weight of the adhesive composition.

58. A process according to claim 46 wherein said hardener for said epoxy resin is an aliphatic amine having at least three active amine hydrogen atoms per molecule.

59. A process according to claim 46 wherein said hardener for said epoxy resin is an amidoamine obtained by reacting a polyamine with a fatty acid.

60. A process according to claim 46 wherein said hardener for said epoxy resin is selected from the group consisting of mercaptans and isocyanates.

61. A process according to claim 46 wherein said hardener for said epoxy resin is an anhydride curing agent.

62. A process according to claim 46 wherein said hardener for said epoxy resin is an aromatic amine.

63. A process according to claim 46 wherein said hardener for said epoxy resin comprises from about 3% to about 15% by weight of the adhesive composition.

64. A process according to claim 46 wherein said catalyst accelerating the curing of said epoxy resin is an alkyl or aryl substituted imidazole catalyst.

65. A process according to claim 46 wherein said catalyst comprises from about 0.3% to about 3% by weight of the adhesive composition.

66. A process according to claim 46 wherein said cross-linking agent reactive with the polyimide solvent is a polyethylenically unsaturated organic compound.

67. A process according to claim 46 wherein said cross-linking agent comprises from about 15% to about 60% by weight of the adhesive composition.

68. A process according to claim 46 wherein said catalyst catalyzing the cross-linking reaction between the polyimide solvent and the cross-linking agent is an organic catalyst having a half life of the same order as the cure time at the temperature chosen.

69. A process according to claim 68 wherein said organic catalyst is an organic peroxide.

70. A process according to claim 68 wherein said organic catalyst is a peroxyketal.

71. A process according to claim 68 wherein said organic catalyst is a t-amyl peroxide.

72. A process according to claim 46 wherein said catalyst catalyzing the cross-linking reaction between the polyimide solvent and the cross-linking agent is 1,1'"'"'-azobis (cyclohexanecarbonitrile).

73. A process according to claim 46 wherein said catalyst catalyzing the cross-linking reaction between the polyimide solvent and the cross-linking agent comprises from about 1.5% to about 15% by weight of the adhesive composition.

74. A process according to claim 46 wherein said filler material comprises glass or silica fillers.

75. A process according to claim 74 wherein said filler is glass.

76. A process according to claim 75 wherein said filler material comprises glass fillers of a size less than 10 microns and preferably of a melting point from about 350°

C. to about 500°

C.

77. A process according to claim 74 wherein said filler is silica.

78. A process according to claim 46 wherein said filler is silica of a size less than 1 micron.

79. A process according to claim 46 wherein said filler material comprises from about 0.3% to about 15% by weight of the adhesive composition.

80. A process according to claim 46, further comprising the addition of a conductive material.

81. A process according to claim 80 wherein the conductive material is a noble metal.

82. A process according to claim 80 wherein the conductive material is a noble metal coated on a non-noble metal.

83. A process according to claim 80 wherein the conductive material comprises from about 55% to about 70% by weight of the reaction mixture.

84. A process according to claim 46 further comprising curing the adhesive composition at about 90°

C. to about 120°

C. for a suitable period of time.

85. A process according to claim 84 comprising curing the adhesive composition at about 90°

C. to about 120°

C. for about 45 minutes.

86. A process according to claim 84 further comprising further curing the adhesive composition at about 200°

C. to about 240°

C. for a suitable period of time.

87. A process according to claim 86 further comprising further curing the adhesive composition at about 200°

C. to about 240°

C. for about 30 minutes.

88. A process according to claim 80 further comprising curing the adhesive composition at about 90°

C. to about 120°

C. for a suitable period of time.

89. A process according to claim 88 comprising curing the adhesive composition at about 90°

C. to about 120°

C. for about 45 minutes.

90. A process according to claim 88 further comprising further curing the adhesive composition at about 200°

C. to about 240°

C. for a suitable period of time.

91. A process according to claim 90 further comprising further curing the adhesive composition at about 200°

C. to about 240°

C. for about 30 minutes.

92. The adhesive composition produced according to the process of claim 46.

93. The adhesive composition produced according to the process of claim 80.

94. The adhesive composition produced according to the process of claim 84.

95. The adhesive composition produced according to the process of claim 86.

96. The adhesive composition produced according to the process of claim 88.

97. The adhesive composition produced according to the process of claim 90.