High temperature adhesive for polymide films

• US 4,859,530 A
• Filed: 07/09/1987
• Issued: 08/22/1989
• Est. Priority Date: 07/09/1987
• Status: Expired due to Fees

• Current Assignee: Ethyl Corporation (Newmarket Corporation)
• Original Assignee: Ethyl Corporation (Newmarket Corporation)
• Inventors: Roark, David N., Lambert, Jules A.
• Primary Examiner(s): Lesmes, George F.
• Assistant Examiner(s): Harbin, A.
• Application Number:
  US07/071,368
• Time in Patent Office: 775 Days
• Field of Search: 428/458, 428/473.5, 428/294, 156/307.3, 156/307.7, 156/311, 156/330.9
• US Class Current: 442/23
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: B32B 15/20 comprising aluminium or copper B32B15/016 and B32B15/017 take precedence
• CPC Class Codes: B32B 2311/12 Copper
• CPC Class Codes: B32B 2379/08 Polyimides
• CPC Class Codes: B32B 27/04 as impregnant, bonding, or embedding substance not used
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/281 comprising polyimides
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C08G 73/105 with oxygen only in the diamino moiety
• CPC Class Codes: C08J 2379/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 5/124 using adhesives based on a macromolecular component
• CPC Class Codes: C08J 5/243 using carbon fibres
• CPC Class Codes: C08J 5/249 characterised by the additives used in the prepolymer mixture
• CPC Class Codes: H05K 3/386 by the use of an organic polymeric bonding layer, e.g. adhesive
• CPC Class Codes: Y10T 428/249951 Including a free metal or alloy constituent
• CPC Class Codes: Y10T 428/31681 Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
• CPC Class Codes: Y10T 428/31721 Of polyimide
• CPC Class Codes: Y10T 442/138 Including a metal layer

Abstract

Thermoplastic polyimides of benzophenone tetracarboxylic acid or an ester or anhydride thereof and a 2,2-bis[4-(amino-phenoxy)phenyl]hexafluoropropane are excellent adhesives for bonding polyimide films to various substrates including polyimide film, metals, etc. The film and substrate need not be abraded before application of the polyamic acid resin or polyimide precursor from which the polyimide is formed on curing. The bond is tenacious. Even after heating to 800° F. the bond was stronger than two different polyimide films. Interposing between the polyimide film and the substrate a strip or patch of a prepreg made from polyimide precursor solutions composed of monomers, solvent and polyamide acid, and applying heat to cure the resin in situ while keeping the components in intimate contact by application of slight pressure is a preferred way of applying and utilizing the adhesives. Such prepregs are also useful for bonding metal to metal or to various other substrates.

Claims

1. A method of bonding a metal to a substrate which comprises placing therebetween a prepreg composed of a fibrous substrate coated and impregnated with a tacky polyimide precursor of (a) a substantially equimolar mixture of (i) 2,2-bis[4-(4-(4aminophenoxy)phenyl]hexafluoropropane or 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, or both, and (ii) lower alkyl diester of benzophenone tetracarboxylic acid;

(b) about 2 to 50 weight percent of polyamic acid polyamide producible from components (i) and (ii); and

(c) about 10 to 50 weight percent of solvent;

applying heat to cause the formation of the polyimide in situ while maintaining the metal and first-named substrate in intimate contact with the curing prepreg; and

then cooling the resultant article.

2. The method of claim 1 in which the 2,2-bis[4[-(aminophenoxy)phenyl]hexafluoropropane of the precursor is 2,2-bis[4-(4-aminophenoxy)]hexafluoropropane.

3. The method claim 1 in which the first-named substrate is a polyimide film.

4. The method of claim 1 in which the first-named substrate is a metal.

5. The method of claim 1 wherein the fibrous substrate of the prepreg is composed of unidirectionally aligned fibers.

6. The method of claim 1 wherein the fibrous substrate of the prepreg is a strip or tape.

7. The method of claim 1 wherein the surfaces of the metal and the substrate between which the prepreg is placed are not pre-abraded.

8. An article produced according to claim 1 wherein the fibrous substrate of the prepreg is composed of unidirectionally aligned fibers.

9. An article produced according to claim 1 wherein the fibrous substrate of the prepreg is a strip or tape.

10. An article produced according to claim 1.

11. An article produced according to claim 1 in which the 2,2-bis[4-(aminophenoxy)phenyl]hexafluoropropane of the precursor is 2,2-bis[4-(4-(aminophenoxy)phenyl)]hexafluoropropane.

12. An article produced according to claim 1 in which the first-named substrate is a polyimide film.

13. An article produced according to claim 1 in which the first-named substrate is a metal.

14. A method of bonding a polyimide film to a substrate which comprises placing therebetween a prepreg composed of a fibrous substrate coated and impregnated with a tacky polyimide precursor of (a) a substantially equimolar mixture of (i) 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane or 2,2-bis[4(3-aminophenoxy)phenyl]hexafluoropropane, or both, and (ii) lower alkyl diester of benzophenone tetracarboxylic acid;

(b) about 2 to 50 weight percent of polyamic acid polyamide producible from components (i) and (ii); and

(c) about 1 to 50 weight percent of solvent;

applying heat to cause the formation of the polyimide in situ while maintaining the polyimide film and first-named substrate in intimate contact with the curing prepreg; and

then cooling the resultant article.

15. The method of claim 14 in which the 2,2-bix[4(aminophenoxy)phenyl]hexafluoropropane of the precursor is 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

16. The method of claim 14 where in the fibrous substrate of the prepreg is composed of unidirectionally aligned fibers.

17. The method of claim 14 wherein the fibrous substrate of the prepreg is a strip or tape.

18. The method of claim 14 wherein the surfaces of the metal and the substrate between which the prepreg is placed are not pre-abraded.

19. The method of claim 14 in which the first-named substrate is a polyimide film.

20. An article produced according to claim 19.

21. The method of claim 14 in which the polyimide film and the substrate are polyimide films of pyromellitic dianhydride and oxydianiline.

22. An article produced according to claim 21.

23. An article produced according to claim 14 wherein the fibrous substrate of the prepreg is composed of unidirectionally aligned fibers.

24. An article produced according to claim 14 wherein the fibrous substrate of the prepreg is a strip or tape.