Resin composition, gasket material and gasket integrated with metal

• US 6,824,730 B2
• Filed: 02/14/2001
• Issued: 11/30/2004
• Est. Priority Date: 02/15/2000
• Status: Expired due to Term

• Current Assignee: Bridgestone Corporation
• Original Assignee: Bridgestone Corporation
• Inventors: Saito, Youkou, Toyosawa, Shinichi, Mashita, Naruhiko, Akasaka, Ichiro, Utsunomiya, Tadashi, Imai, Yasushi, Nishimuro, Youichi
• Primary Examiner(s): MULLIS, JEFFREY C
• Application Number:
  US09/784,415
• Publication Number:
  US 20010018490A1
• Time in Patent Office: 1,385 Days
• Field of Search: 264/480, 264/483, 428/461, 428/462, 428/457, 525/71
• US Class Current: 264/480
• CPC Class Codes: B29C 45/14811 Multilayered articles B29C45/14827 takes precedence
• CPC Class Codes: B29K 2705/00 Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
• CPC Class Codes: B29L 2031/265 Packings, Gaskets
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 53/025 modified
• CPC Class Codes: Y10T 428/31692 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31696 Including polyene monomers [e.g., butadiene, etc.]

Abstract

There are disclosed a resin composition which is excellent in rubber elasticity, oil maintainability and adhesivity to a metal, and comprises a thermoplastic elastomer composition comprising a (a1) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of a polymer block composed principally of a vinyl aromatic compound and a polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 200,000, in which the polymer block composed principally of a vinyl aromatic compound is polystyrene, and in which the content by weight of the polystyrene moiety contained in the hydrogenated block copolymer is 20 to 40%; a (b1) non-aromatic rubber-softening agent having a kinematic viscosity at 40° C. of at least 300 mm²s⁻¹; and a (c1) modified polyolefinic resin, the resin composition having a hardness according to JIS K6253 of at most 50 degrees and a compression set according to JIS K6262 of at most 50%; a composite molded body of a metal and the thermo-plastic elastomer composition such as a gasket integrated with a metallic sheet; and processes for producing the above products.

Claims

1. A resin composition which comprises a thermoplastic elastomer composition comprising 100 parts by weight of a (a1) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 300,000, in which the at least one polymer block composed principally of a vinyl aromatic compound is polystyrene, and in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

100 to 200 parts by weight of a (b1) non-aromatic rubber softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup> and 10 to 50 parts by weight of a (c1) modified polyolefinic resin, said resin composition having a hardness as measured in accordance with JIS K6253 with durometer of type A being at most 50 degrees and a compression set as measured in accordance with JIS K6262 after being allowed to stand at 70°

C. under a compression ratio of 25% for 22 hours being at most 50%, wherein the (c1) modified polyolefinic resin is that which has a functional group having an absorption band at a wave number in the range of 1500 to 2000 cm<sup>−

1</sup> in the infrared absorption spectrum thereof.

2. The resin composition according to claim 1, wherein the (c1) modified polyolefinic resin is a resin which is produced by modifying a polyolefinic resin composed principally of polypropylene with an unsaturated carboxylic acid or a derivative thereof.

3. The resin composition according to claim 2, wherein the unsaturated carboxylic acid is maleic anhydride.

4. A gasket material which comprises the resin composition as set forth in claim 1.

5. A gasket integrated with a metal, which is formed by molding the gasket material as set forth in claim 4.

6. A hard disc gasket which comprises the gasket integrated with a metal as set forth in claim 5.

22. A hard disc gasket, which comprises the gasket integrated with a metal as set forth in claim 4.

7. A thermoplastic elastomer composition comprising 100 parts by weight of a (a2) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 300,000, in which the at least one polymer block composed principally of a vinyl aromatic compound is polystyrene and in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

100 to 200 parts by weight of a (b2) non-aromatic rubber softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup>; and

10 to 50 parts by weight of a (c2) modified hydrogenated block copolymer obtained by hydrogenating a block copolymer in which a functional group is imparted to a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound; and

0 to 20 parts by weight of a (d2) compound composed principally of a crystalline polyolefin, said thermoplastic elastomer composition having a hardness as measured in accordance with JIS K6253 with a durometer of type A being at most 50 degrees and a compression set as measured in accordance with JIS K6262 after being allowed to stand at 70°

C. under a compression ratio of 25% for 22 hours being at most 50%,

wherein the (c2) modified hydrogenated block copolymer is that which has a functional group having an absorption band at a wave number in the range of 1500 to 2000 cm<sup>−

1</sup> in the infrared absorption spectrum thereof.

8. The thermoplastic elastomer composition according to claim 7, wherein the (c2) modified hydrogenated block copolymer is that which is modified with an unsaturated carboxylic acid or a derivative thereof.

9. The thermoplastic elastomer composition according to claim 8, wherein the unsaturated carboxylic acid is maleic anhydride.

10. A gasket material which comprises the thermoplastic elastomer composition as set forth in claim 7.

11. A gasket, comprising the gasket material of claim 10, wherein said gasket material is integrated with a metallic cover or a metallic frame.

12. A gasket for a hard disc apparatus, comprising the gasket material of claim 10, wherein said gasket material is integrated with a metallic cover or a metallic frame.

13. A composite molded body, prepared by a process comprising integrating through thermally fusing adhesion, a metallic sheet laminated with a thermoplastic resin having a hardness as measured in accordance with JIS 6253 with a durometer of type A of at least 50 degrees;

and a thermoplastic elastomer composition comprising said resin composition according to claim 7.

14. The composite molded body according to claim 13, wherein the thermoplastic elastomer composition comprises 100 parts by weight of a (a3) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of polystyrene block and at least one polymer block composed principally of a conjugated diene compound, in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

100 to 500 parts by weight of a (b3) non-aromatic softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup>; and

5 to 100 parts by weight of a (c3) polyolefinic hydrocarbon resin.

15. A gasket fitted to a cover with the use of the composite molded body according to claim 13.

16. The gasket fitted to a cover according to claim 15, comprising a metal surface side of said metallic sheet, and wherein said metal surface side of said metallic sheet forms a sealing surface.

17. The composite molded body according to claim 13, wherein the thermoplastic resin is at least one species selected from the group consisting of polyethylene, polypropylene and polystyrene.

18. The composite molded body according to claim 13, wherein the thermoplastic resin laminate has a thickness of at most 100 μ

m.

19. The composite molded body according to claim 13, wherein the thermoplastic elastomer composition comprises at least one species selected from the group consisting of styrenic thermoplastic elastomers, olefinic thermoplastic elastomers and urethanic thermoplastic elastomers.

20. A process for producing the composite molded body as set forth in claim 13, comprising placing a metallic sheet which has a prescribed shape and which is laminated on at least one side thereof with a thermoplastic resin, and injection molding a thermoplastic elastomer composition onto at least one part of the surface laminated therewith to integrate the metallic sheet and the thermoplastic elastomer composition.

21. A gasket, comprising a gasket material integrated with a metal, which is formed by molding said gasket material,

wherein said gasket material comprises a resin composition, and

wherein said resin composition comprises a thermoplastic elastomer composition comprising 100 parts by weight of a (a1) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 200,000, in which the at least one polymer block composed principally of a vinyl aromatic compound is polystyrene, and in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

100 to 200 parts by weight of a (bi) non-aromatic rubber-softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup>; and

10 to 50 parts by weight of a (c1) modified polyolefinic resin, said resin composition having a hardness as measured in accordance with JIS K6253 with a durometer of type A being at most 50 degrees and a compression set as measured in accordance with JIS K6262 after being allowed to stand at 70°

C. under a compression ratio of 25% for 22 hours being at most 50%.

23. A gasket, comprising a gasket material integrated with a metal, which is formed by molding said gasket material into a gasket integrated with a metallic cover or a metallic frame,

wherein said gasket material comprises a thermoplastic elastomer composition, and

wherein said thermoplastic elastomer composition comprises 100 parts by weight of a (a2) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 200,000, in which the at least one polymer block composed principally of a vinyl aromatic compound is polystyrene and in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

100 to 200 parts by weight of a (b2) non-aromatic rubber-softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup>;

10 to 50 parts by weight of a (c2) modified hydrogenated block copolymer obtained by hydrogenating a block copolymer in which a functional group is imparted to a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound; and

0 to 20 parts by weight of a (d2) compound composed principally of a crystalline polyolefin, said thermoplastic elastomer composition having a hardness as measured in accordance with JIS K6253 with a durometer of type A being at most 50 degrees and a compression set as measured in accordance with JIS K6262 after being allowed to stand at 70°

C. under a compression ratio of 25% for 22 hours being at most 50%.

24. The gasket according to claim 23, which is a hard disc apparatus.

25. A process for producing a gasket integrated with a cover, comprising placing a metallic cover in a mold, and injecting a gasket material composed of a thermoplastic elastomer composition onto the surface of said cover so as to form a gasket portion, wherein the thermoplastic elastomer composition is injection cast from a direction different from the direction towards a butt contact surface on the gasket portion upon the use thereof, and wherein the thermoplastic elastomer composition comprises 100 parts by weight of a (a6) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 150,000, in which the at least one polymer block composed principally of a vinyl aromatic compound is polystyrene, and in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

50 to 200 parts by weight of a (b6) non-aromatic rubber-softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup>; and

5 to 50 parts by weight of a (c6) polyolefinic resin composed principally of polypropylene, said thermoplastic elastomer composition having a hardness as measured in accordance with JIS K6253 with durometer of type A being at most 50 degrees and a compression set measured in accordance with JIS K6262 after being allowed to stand at 70°

C. under a compression ratio of 25% for 22 hours being at most 50%.

26. A process for producing a gasket integrated with a cover, comprising placing a metallic cover in a mold, and injecting a gasket material composed of a thermoplastic elastomer composition onto the surface of said cover so as to form a gasket portion, wherein the thermoplastic elastomer composition is injection cast from a direction different from the direction towards a butt contact surface on the gasket portion upon the use thereof, and wherein the thermoplastic elastomer composition comprises 100 parts by weight of a (a7) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 200,000, in which the at least one polymer block composed principally of a vinyl aromatic compound is polystyrene, and in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

100 to 200 parts by weight of a (b7) non-aromatic rubber-softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup>; and

10 to 50 parts by weight of a (c7) modified polyolefinic resin, said thermoplastic elastomer composition having a hardness as measured in accordance with JIS K6253 with durometer of type A being at most 50 degrees and a compression set as measured in accordance with JIS K6262 after being allowed to stand at 70 °

C. under a compression ratio of 25% for 22 hours being at most 50%.

27. The process for producing a composite molded body of a resin and metal according to claim 26, wherein the (c7) modified polyolefinic resin is a polyolefinic resin composed principally of polyethylene or polypropylene and contains an unsaturated carboxylic acid or a derivative thereof or acrylic acid or a derivative thereof.

28. The process for producing a composite molded body of a resin and metal according to claim 27, wherein the unsaturated carboxylic acid is maleic anhydride.

29. A process for producing a composite molded body of a resin and metal which comprises subjecting part or all of the surface of a metallic part that comes into contact with a resin portion to a corona treatment or a plasma treatment, thereafter placing the metallic part thus treated in a mold, and then injecting a thermoplastic elastomer composition onto the surfaces of the metallic part placed in the mold to form the resin portion.

30. The process for producing a composite molded body of a resin and metal according to claim 29, wherein the thermoplastic elastomer composition comprises 100 parts by weight of a (a4) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 150,000, in which the at least one polymer block composed principally of a vinyl aromatic compound is polystyrene and in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

50 to 200 parts by weight of a (b4) non-aromatic rubber-softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup>; and

5 to 50 parts by weight of a (c4) polyolefinic resin composed principally of polypropylene, said thermoplastic elastomer composition having a hardness as measured in accordance with JIS K6253 with a durometer of type A being at most 50 degrees and a compression set as measured in accordance with JIS K6262 after being allowed to stand at 70°

C. under a compression ratio of 25% for 22 hours being at most 50%.

31. The process for producing a composite molded body of a resin and metal according to claim 29, wherein the thermoplastic elastomer composition comprises 100 parts by weight of a (a5) hydrogenated block copolymer which is obtained by hydrogenating a block copolymer consisting essentially of at least one polymer block composed principally of a vinyl aromatic compound and at least one polymer block composed principally of a conjugated diene compound, which has a weight average molecular weight of at least 200,000, in which the at least one polymer block composed principally of a vinyl aromatic compound is polystyrene and in which the content by weight of the polystyrene moiety that is contained in the hydrogenated block copolymer is in the range of 20 to 40%;

100 to 200 parts by weight of a (b5) non-aromatic rubber-softening agent having a kinematic viscosity at 40°

C. of at least 300 mm²s<sup>−

1</sup>; and

10 to 50 parts by weight of a (c5) modified polyolefinic resin, said thermoplastic elastomer composition having a hardness as measured in accordance with JIS K6253 with a durometer of type A being at most 50 degrees and a compression set as measured in accordance with JIS K6262 after being allowed to stand at 70°

C. under a compression ratio of 25% for 22 hours being at most 50%.

32. The process for producing a composite molded body of a resin and metal according to claim 31, wherein the (c5) modified polyolefinic resin is a polyolefinic resin composed principally of polyethylene or polypropylene, and contains an unsaturated carboxylic acid or a derivative thereof or acrylic acid or a derivative thereof.

33. The process for producing a composite molded body of a resin and metal according to claim 32, wherein the unsaturated carboxylic acid is maleic anhydride.

34. A composite molded body of a resin and metal, characterized by being produced by the process as set forth in claim 29.

35. The composite molded body of a resin and metal according to claim 34, which is a gasket integrated with a cover.

36. A process for producing a gasket integrated with a cover, comprising placing a metallic cover in a mold, and injecting a gasket material composed of a thermoplastic elastomer composition onto the surface of said cover so as to form a gasket portion, wherein the thermoplastic elastomer composition is injection cast from a direction different from the direction towards a butt contact surface on the gasket portion upon the use thereof, and wherein the thermoplastic elastomer composition is injection cast onto the surface of the cover from the direction towards the rear face of the gasket portion through at least one hole bored in advance in the metallic cover.

37. A process for producing a gasket integrated with a cover, comprising placing a metallic cover in a mold, and injecting a gasket material composed of a thermoplastic elastomer composition onto the surface of said cover so as to form a gasket portion, wherein the thermoplastic elastomer composition is injection cast from a direction different from the direction towards a butt contact surface on the gasket portion upon the use thereof, and wherein the thermoplastic elastomer composition is injection cast onto the surface of the cover from the direction towards a side face of the gasket portion.