Modified polyimide resin and curable resin composition

• US 7,687,113 B2
• Filed: 09/09/2005
• Issued: 03/30/2010
• Est. Priority Date: 09/10/2004
• Status: Active Grant

• Current Assignee: UBE Industries Limited
• Original Assignee: UBE Industries Limited
• Inventors: Hirano, Tetsuji, Kinouchi, Masayuki, Maeda, Shuichi, Naiki, Masahiro, Takasawa, Ryoichi
• Primary Examiner(s): CAMERON, ERMA C
• Application Number:
  US11/658,314
• Publication Number:
  US 20080311303A1
• Time in Patent Office: 1,663 Days
• Field of Search: None
• US Class Current: 427/385.5
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/3846 containing imide groups C08G18/3821 takes precedence
• CPC Class Codes: C08G 18/44 Polycarbonates
• CPC Class Codes: C08G 18/58 Epoxy resins C08G18/42, C08G18/48 take precedence; reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen C08G18/6407, with at least equivalent amounts of amines C08G18/6415; polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen C08G18/003
• CPC Class Codes: C08G 18/69 Polymers of conjugated dienes hydrogenated polymers of conjugated dienes C08G18/6208
• CPC Class Codes: C08G 18/8077 Oximes
• CPC Class Codes: C08G 73/14 Polyamide-imides
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: H05K 1/0346 containing N
• CPC Class Codes: H05K 3/285 Permanent coating compositions
• CPC Class Codes: H05K 3/4676 Single layer compositions

Abstract

A modified polyimide resin favorably employable for manufacturing an insulation film of an electric-electronic device is composed of recurring units (I) derived from a biphenyltetracarboxylic acid compound, a diamine compound, and a monoamine compound having at least one hydroxyl group and recurring units (II) derived from diisocyanate and polybutadiene having hydroxyl group at each terminal, which optionally contains further recurring units (III) derived from diisocyanate and a compound having hydroxyl group at each terminal and further having a reactive substituent.

Claims

1. A polyimide resin comprising the following recurring units (I) and (II):

2. The polyimide resin of claim 1, in which R¹ is a tetravalent residue obtained from a tetracarboxylic acid compound selected from the group consisting of 2,3,3′

,4′

-biphenyltetracarboxylic acid, 3,3′

,4,4′

-diphenylethertetracarboxylic acid, 2,2′

,3,3′

-biphenyltetracarboxylic acid, 2,3,3′

,4′

-biphenyltetracarboxylic acid dianhydride, 3,3′

,4,4′

-diphenylethertetracarboxylic acid dianhydride, 2,2′

,3,3′

-biphenyltetracarboxylic acid dianhydride, an ester of 2,3,3′

,4′

-biphenyltetracarboxylic acid, an ester of 3,3′

,4,4′

-diphenylethertetracarboxylic acid, and an ester of 2,2′

,3,3′

-biphenyltetracarboxylic acid.

3. The polyimide resin of claim 1, in which R² is an alicyclic group having 4 to 20 carbon atoms.

4. The polyimide resin of claim 1, in which R³ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

5. The polyimide resin of claim 1, in which R⁴ is a divalent polybutadiene unit having a number average molecular weight in the range of 500 to 10,000.

6. The polyimide resin of claim 1, in which R⁶ is a divalent hydrocarbon group selected from the group consisting of a divalent aliphatic group, a divalent alicyclic group, a divalent aromatic group, and combinations thereof.

14. A method for preparing the polyimide resin of claim 1 which comprises reacting a diisocyanate compound having the formula (1), a polybutadiene compound having the formula (2), and an imide compound having the formula (3):

17. A curable polyimide resin composition comprising 100 weight parts of a polyimide resin of claim 1, 1 to 50 weight parts of an epoxy group, and an organic solvent.

18. The curable polyimide resin composition of claim 17, which further comprises a blocked polyvalent isocyanate compound.

19. The curable polyimide resin composition of claim 17, which further comprises a polycarbonate compound having a hydroxyl group at each terminal.

20. The curable polyimide resin composition of claim 17, which further comprises a compound having a phenolic hydroxyl group.

21. A curable polyimide resin composition comprising 100 weight parts of a polyimide resin of claim 7, 1 to 50 weight parts of an epoxy group, and an organic solvent.

22. The curable polyimide resin composition of claim 21, which further comprises a blocked polyvalent isocyanate compound.

23. The curable polyimide resin composition of claim 21, which further comprises a polycarbonate compound having a hydroxyl group at each terminal.

24. The curable polyimide resin composition of claim 21, which further comprises a compound having a phenolic hydroxyl group.

25. A process for preparing a cured resin film which comprises the steps of coating a curable polyimide resin composition of claim 17 on a substrate and heating the coated composition.

26. A process for preparing a cured resin film which comprises the steps of coating a curable polyimide resin composition of claim 21 on a substrate and heating the coated composition.

7. A polyimide resin comprising the following recurring units (I), (II), and (III):

8. The polyimide resin of claim 7, in which R¹ is a tetrava lent residue obtained from a tetracarboxylic acid compound selected from the group consisting of 2,3,3′

,4′

-biphenyltetracarboxylic acid, 3,3′

,4,4′

-diphenylethertetracarboxylic acid, 2,2′

,3,3′

-biphenyltetracarboxylic acid, 2,3,3′

,4′

-biphenyltetracarboxylic acid dianhydride, 3,3′

,4,4′

-diphenylethertetracarboxylic acid dianhydride, 2,2′

,3,3′

-biphenyltetracarboxylic acid dianhydride, an ester of 2,3,3′

,4′

-biphenyltetracarboxylic acid, an ester of 3,3′

,4,4′

-diphenylethertetracarboxylic acid, and an ester of 2,2′

,3,3′

-biphenyltetracarboxylic acid.

9. The polyimide resin of claim 7, in which R² is an alicyclic group having 4 to 20 carbon atoms.

10. The polyimide resin of claim 7, in which R³ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

11. The polyimide resin of claim 7, in which R⁴ is a divalent polybutadiene unit having a number average molecular weight in the range of 500 to 10,000.

12. The polyimide resin of claim 7, in which R⁵ is a divalent hydrocarbon group having a carboxyl group.

13. The polyimide resin of claim 7, in which R⁶ is a divalent hydrocarbon group selected from the group consisting of a divalent aliphatic group, a divalent alicyclic group, a divalent aromatic group, and combinations thereof.

15. A method for preparing the polyimide resin of claim 7 which comprises reacting a diisocyanate compound having the formula (1), a polybutadiene compound having the formula (2), a divalent compound having the formula (4), and an imide compound having the formula (3):

16. A method for preparing the polyimide resin of claim 7 which comprises reacting a divalent isocyanate compound having the formula (5) and an imide compound having the formula (3):

27. An imide oligomer having the following formula (3):