Benzoxazines, thermosetting resins comprised thereof, and methods for use thereof

• US 6,743,852 B2
• Filed: 11/13/2001
• Issued: 06/01/2004
• Est. Priority Date: 11/13/2001
• Status: Active Grant

• Current Assignee: Henkel IP & Holding GmbH (Henkel AG & Co KGaA)
• Original Assignee: Henkel Corporation (Henkel AG & Co KGaA)
• Inventors: Mizori, Farhad G., Dershem, Stephen M., Liu, Puwei
• Primary Examiner(s): Raymond, Richard L.
• Application Number:
  US10/008,591
• Publication Number:
  US 20030125551A1
• Time in Patent Office: 931 Days
• Field of Search: 544/73, 544/90, 544/95, 524/548, 526/256, 526/262
• US Class Current: 524/548
• CPC Class Codes: C07D 265/16 with only hydrogen or carbon atoms directly attached in positions 2 and 4
• CPC Class Codes: C07D 413/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

In accordance with the present invention, there are provided novel benzoxazine compounds and thermosetting resin compositions prepared therefrom. Invention compositions are particularly useful for increasing adhesion at interfaces within microelectronic packages. Invention benzoxazines are useful for the preparation of invention compositions with properties which are associated with increased adhesion at interfaces, such as, for example, low shrinkage on cure and low coefficient of thermal expansion (CTE). In another aspect of the invention, there are provided die-attach pastes having increased interfacial adhesion. Invention die-attach pastes include benzoxazine-containing thermosetting resin compositions. In further aspects of the invention, there are provided methods for enhancing adhesive strength of thermosetting resin compositions and methods for enhancing adhesion of a substrate bound to a metallic surface by a thermosetting resin composition.

Claims

1. A compound having the structure:

wherein;

L is an optional alkylene or siloxane linking moiety,

Ar is optionally substituted arylene,

Q is an oxazine ring or amine salt thereof having the structure;

and is bonded to Ar in a fused manner at positions 5 and 6 of the oxazine ring,

wherein;

Sp is optional, and if present, is a C₁ to C₆ alkylene, oxyalkylene, thioalkylene, carboxyalkylene, amidoalkylene, or sulfonatoalkylene spacer,

n is 1 or 2,

m is 1 or 2,

x and y are each independently 0 to 4, and

wherein at least one of R, R′

, or R″

is a polymerizable moiety independently selected from the group consisting of opti nally substituted oxyalkenyl, alkynyl, cycloalkenyl, bicycloalkenyl, styryl, (meth)acrylate, itaconate, maleimide, vinyl ester, epoxy, cyanate ester, nitrile, diallyl amide, benzocyclobutene, aromatic propargyl ether, aromatic acetylene and oxazoline, and the remainder of R, R′ and

R″

is(are) independently selected from the group consisting of hydrogen, alkyl and alkoxy.

2. A compound according to claim 1 having the structure:

3. A compound according to claim 1, wherein said polymerizable moiety participates in an addition polymerization.

4. A compound according to claim 3, wherein said addition polymerization is a free-radical polymerization, anionic polymerization, cationic polymerization, or ring-opening polymerization.

5. A compound according to claim 1, wherein said polymerizable moiety is oxyalkenyl, (meth)acrylate, maleimide, or cycloalkenyl.

6. A compound according to claim 2, wherein said polymerizable moiety participates in an addition polymerization.

7. A compound according to claim 6, wherein said addition polymerization is a free-radical polymerization, anionic polymerization, cationic polymerization, or ring-opening polymerization.

8. A compound according to claim 2, wherein said polymerizable moiety is oxyalkenyl, (meth)acrylate, maleimide, or cycloalkenyl.

9. A compound according to claim 2, wherein optionally substituted Ar is phenylene or naphthylene.

10. A compound according to claim 9, wherein optionally substituted Ar is phenylene.

11. A compound according to claim 9, wherein Ar is naphthylene.

12. A compound according to claim 1, wherein L is alkylene.

13. A compound according to claim 1, wherein L is siloxane.

14. An adhesive composition comprising a compound according to claim 1 and a curing catalyst.

15. An adhesive composition according to claim 14, further comprising one or more co-reactants.

16. An adhesive composition according to claim 15, wherein said co-reactants are maleimide, epoxy, urethane, or cyanate eater.

17. An adhesive composition according to claim 16, wherein said maleimide is a liquid maleimide.

18. An adhesive composition according to claim 17, wherein said liquid maleimide has the structure:

wherein;

m is 1-3,

each R is independently hydrogen or lower alkyl, and

X is a saturated straight chain alkyl, alkylene, or alkylene oxide, or branched chain alkyl, alkylene or alkylene oxide, optionally containing saturated cyclic moieties as substituents on said alkyl, alkylene or alkylene oxide chain or as part of the backbone of the alkyl, alkylene or alkylene oxide chain.

19. A thermosetting resin composition comprising:

A) a compound according to claim 1,

B) a liquid maleimide,

C) a coupling agent, and

D) a cure initiator.

20. A die-attach paste comprising:

in range of about 10 up to 80 wt % of a thermosetting resin composition according to claim 19, and

in the range of about 20 up to about 90 wt % of a filler.

21. A die-attach paste according to claim 20, wherein the filler is conductive.

22. A die-attach paste according to claim 21, wherein said filler is electrically conductive.

23. A die-attach paste according to claim 21, wherein said filler is thermally conductive.

24. A method for enhancing adhesive strength of a thermosetting resin composition, said method comprising incorporating an effective amount of a compound according to claim 1 into said composition.

25. A method for enhancing adhesion of a substrate bound to a metallic surface by a thermosetting resin composition, said method comprising incorporating a compound according to claim 1 into said thermosetting resin composition.

26. A method according to claim 25, wherein said metallic surface is copper.

27. A method for adhesively attaching a substrate to a metallic surface, said method comprising curing a die-attach paste positioned between said substrate and said metallic surface, wherein said die-attach paste comprises a compound according to claim 1.

28. A method according to claim 27, wherein said substrate is a semiconductor die and said metallic surface is a lead frame.

29. A method according to claim 28, wherein said lead frame is a copper lead frame.