PTC conductive polymer composition containing carbon black having large particle size and high DBP absorption

• US 5,174,924 A
• Filed: 06/04/1990
• Issued: 12/29/1992
• Est. Priority Date: 06/04/1990
• Status: Expired due to Fees

• Current Assignee: Fujikura Limited
• Original Assignee: Fujikura Limited
• Inventors: Isshiki, Setsuya, Yamada, Makoto, Kurosawa, Yukihiko
• Primary Examiner(s): Lieberman, Paul
• Assistant Examiner(s): SWOPE, BRADLEY
• Application Number:
  US07/532,712
• Time in Patent Office: 939 Days
• Field of Search: 252/511, 252/510, 524/495, 524/496, 423/445
• US Class Current: 252/511
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: H01B 1/24 the conductive material comprising carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01C 7/027 consisting of conducting or semi-conducting material dispersed in a non-conductive organic material

Abstract

A conductive polymer composition exhibiting positive temperature coefficient behavior comprising:

(a) a crystalline polymer having dispersed therein

(b) carbon black having an average particle diameter of at least about 60 millimicrons and a DBP absorption of at least about 80 cc/100 g.

Circuit protection devices containing a thin layer of this conductive polymer composition between laminar electrodes provide high breakdown voltage in combination with very low resistance and are useful for protecting high-current/high voltage battery-powered devices.

Claims

1. A conductive polymer composition exhibiting positive temperature coefficient behavior and an improved breakdown voltage property, comprising:

(a) a crystalline polymer having a crystallinity of about 10 to 98 percent and having dispersed therein

(b) carbon black having an average particle diameter of from about 80 to 110 millimicrons and a DBP absorption of from about 110 to 140 cc/100 g,

wherein said composition comprises 100 parts by weight of said crystalline polymer and 40 to 150 parts by weight of said carbon black.

2. The conductive polymer composition as claimed in claim 1, wherein said crystalline polymer has a crystallinity of at least about 20 percent.

3. The conductive polymer composition as claimed in claim 1, wherein said crystalline polymer has a crystallinity of about 20 to 40 percent.

4. The conductive polymer composition as claimed in claim 1, wherein said crystalline polymer comprises a polyolefin comprising at least one α

-olefin.

5. The conductive polymer composition as claimed in claim 4, wherein said crystalline polymer is selected from the group consisting of polyethylene, polypropylene and a copolymer of ethylene and propylene.

6. The conductive polymer composition as claimed in claim 5, wherein said crystalline polymer is modified to contain at least one maleic acid, epoxy or isocyanate group.

7. The conductive polymer composition as claimed in claim 4, wherein said crystalline polymer comprises a copolymer of an α

-olefin and at least one polar comonomer.

8. The conductive polymer composition as claimed in claim 7, wherein said polar comonomer is selected from the group consisting of vinyl acetate, acrylic acid, an acrylic acid salt, methacrylic acid, a methacrylic acid salt, ethyl acrylic acid, an ethyl acrylic acid salt, ethyl acrylate, and methacrylate.

9. The conductive polymer composition as claimed in claim 8, wherein said crystalline polymer is modified to contain at least one maleic acid, epoxy, or isocyanate group.

10. The conductive polymer composition as claimed in claim 1, wherein said crystalline polymer comprises a polyester.

11. The conductive polymer composition as claimed in claim 10, wherein said polyester is selected from polybutylene terephthalate, polyethylene terephthalate, and polycaprolactone.

12. The conductive polymer composition as claimed in claim 1, wherein said crystalline polymer comprises at least one of a polyarylene, a polyamide, and a polycarbonate.

13. The conductive polymer composition as claimed in claim 1, wherein said crystalline polymer comprises a fluorocarbon polymer.

14. The conductive polymer composition as claimed in claim 13, wherein said fluorocarbon polymer is selected from the group consisting of polyvinylidene fluoride, polytetrafluoroethylene, a fluorinated copolymer of ethylene and propylene, and a copolymer of ethylene and a comonomer containing fluorine.

15. The conductive polymer composition as claimed in claim 4, wherein said crystalline polymer comprises a copolymer of ethylene and at least one copolymerizable monomer comprising an ester group or a carboxyl group.

16. The conductive polymer composition as claimed in claim 15, wherein said copolymer comprises at least one epoxy group or isocyanate group.

17. The conductive polymer composition as claimed in claim 8, wherein said crystalline polymer is a copolymer of ethylene and at least one copolymerizable monomer selected from the group consisting of acrylic acid, vinyl acetate, and methacrylic acid.

18. The conductive polymer composition as claimed in claim 17, wherein said copolymer comprises from about 80 to less than 100 percent of ethylene and from more than 0 to about 25% of said copolymerizable monomer.

19. The conductive polymer composition as claimed in claim 5, wherein said crystalline polymer is polyethylene.

20. The conductive polymer composition as claimed in claim 19, wherein said crystalline polymer is high density polyethylene.

21. The conductive polymer composition as claimed in claim 7, wherein said crystalline polymer is an ionomeric copolymer comprising ethylene, methacrylic acid and a methacrylic acid salt.

22. The conductive polymer composition as claimed in claim 7, wherein said crystalline polymer is a terpolymer of ethylene, vinyl acetate and glycidyl methacrylate.

23. The conductive polymer composition as claimed in claim 7, comprising 100 parts by weight of said crystalline polymer and from about 50 to 150 parts by weight of said carbon black.

24. The conductive polymer composition as claimed in claim 1, comprising 100 parts by weight of said crystalline polymer and from about 50 to 120 parts by weight of said carbon black.

25. The conductive polymer composition as claimed in claim 19, comprising 100 parts by weight of said crystalline polymer and from about 40 to 120 parts by weight of said carbon black.

26. The conductive polymer composition as claimed in claim 20, comprising 100 parts by weight of said crystalline polymer and from about 50 to 110 parts by weight of said carbon black.

27. The conductive polymer composition as claimed in claim 26, comprising 100 parts by weight of said crystalline polymer and from about 65 to 85 parts by weight of said carbon black.

28. The conductive polymer composition as claimed in claim 21, comprising 100 parts by weight of said crystalline polymer and from about 60 to 120 parts by weight of said carbon black.

29. The conductive polymer composition as claimed in claim 28, comprising 100 parts by weight of said crystalline polymer and from about 70 to 100 parts by weight of said carbon black.

30. The conductive polymer composition as claimed in claim 22, comprising 1200 parts by weight of said crystalline polymer and from about 60 to 120 parts by weight of said carbon black.

31. The conductive polymer composition as claimed in claim 30, comprising 100 parts by weight of said crystalline polymer and from about 70 to 100 parts by weight of said carbon black.

32. The conductive polymer composition as claimed in claim 1, wherein said composition has a volume resistivity of at most about 100 Ω

-cm at a temperature between -40°

C. and a switching temperature T_s of said composition.

33. The conductive polymer composition as claimed in claim 32, wherein said composition has a volume resistivity of at most about 50 Ω

-cm at a temperature between -40°

C. and a switching temperature T_s of said composition.

34. The conductive polymer composition as claimed in claim 33, wherein said composition has a volume resistivity of at most about 20 Ω

-cm at a temperature between -40°

C. and a switching temperature T_s of said composition.

35. The conductive polymer composition as claimed in claim 34, wherein said composition has a volume resistivity of at most about 10 Ω

-cm at a temperature between -40°

C. and a switching temperature T_s of said composition.

36. The conductive polymer composition as claimed in claim 32, wherein said composition has a peak resistivity of at least about 1000 Ω

·

cm.

37. The conductive polymer composition as claimed in claim 36, wherein said composition has a peak resistivity of at least about 5000 Ω

·

cm.

38. The conductive polymer composition as claimed in claim 37, wherein said composition has a peak resistivity of at least about 10,000 Ω

·

cm.

39. The conductive polymer composition as claimed in claim 38, wherein said composition has a peak resistivity of at least about 50,000 Ω

·

cm.

40. The conductive polymer composition as claimed in claim 1, wherein the volume ratio of said carbon black to said crystalline polymer is from 0.15 to 0.65.

41. The conductive polymer composition as claimed in claim 1, wherein the specific surface area S of said carbon black in m² /g and the average particle diameter D of said carbon black are such that S/D is at most about 10.

42. The conductive polymer composition as claimed in claim 41, wherein the quantity ##EQU4## is at most about 1.0.

43. The conductive polymer composition as claimed in claim 1, having a switching temperature T_s of at most about 180°

C.

44. The conductive polymer composition as claimed in claim 43, having a switching temperature T_s of at most about 130°

C.

45. The conductive polymer composition as claimed in claim 44, having a switching temperature T_s of at most about 100°

C.

46. The conductive polymer composition as claimed in claim 1, wherein said crystalline polymer is crosslinkable.