Composite and process for producing the same

• US 20030170469A1
• Filed: 09/16/2002
• Published: 09/11/2003
• Est. Priority Date: 01/16/2001
• Status: Active Grant

• Current Assignee: Daicel-Degussa Limited
• Original Assignee: Daicel-Degussa Limited
• Inventors: Ikuta, Toru, Mutsuda, Mitsuteru, Komada, Hajime
• Granted Patent: US 6,800,372 B2
• Time in Patent Office: Days
• US Class Current: 428/447
• CPC Class Codes: B29C 45/1676 using a soft material and a rigid material, e.g. making articles with a sealing part
• CPC Class Codes: B29K 2083/005 LSR, i.e. liquid silicone rubbers, or derivatives thereof
• CPC Class Codes: B29K 2221/003 Thermoplastic elastomers
• CPC Class Codes: B32B 2038/0076 Curing, vulcanising, cross-linking
• CPC Class Codes: B32B 2319/00 Synthetic rubber natural rubber B32B2317/22
• CPC Class Codes: B32B 2367/00 Polyesters, e.g. PET, i.e. polyethylene terephthalate
• CPC Class Codes: B32B 2369/00 Polycarbonates
• CPC Class Codes: B32B 2375/00 Polyureas; Polyurethanes
• CPC Class Codes: B32B 2377/00 Polyamides
• CPC Class Codes: B32B 2379/08 Polyimides
• CPC Class Codes: B32B 2398/20 Thermoplastics
• CPC Class Codes: B32B 25/08 of synthetic resin
• CPC Class Codes: B32B 25/20 comprising silicone rubber
• CPC Class Codes: B32B 2605/08 Cars
• CPC Class Codes: C08J 2383/04 Polysiloxanes
• CPC Class Codes: C08J 5/12 Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31667 Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Abstract

A composite of a resin member bonded to a rubber member is obtained by molding a resin molding element and a rubber molding element with contacting said elements each other, and vulcanizing or crosslinking the rubber molding element, wherein said resin molding element is either of a resin composition and a resin member, each comprising the thermoplastic resin; and said rubber molding element is either of a rubber composition and a rubber premolded article, each comprising at least an unvulcanized silicone rubber, and a radical-generating agent (e.g., organic peroxides) being activating on a surface to be contacted with said resin molding element. The thermoplastic resin includes a polyamide-series resin, a polyester-serires resin, a PPE-series resin, etc. The unvulcanized rubber composition may comprise a polyfunctional compound having plural polymerizable groups. Such a process can give a composite composed of a thermoplastic resin molded article bonded to a vulcanized silicone rubber molded article directly and firmly without an adhesive treatment.

Claims

1. A composite of a vulcanized silicone rubber member formed by a vulcanization of an unvulcanized silicone rubber, and resin member comprising a thermoplastic resin and directly bonded to the rubber member, wherein the resin member bonds directly to the vulcanized silicone rubber member vulcanized or crosslinked with a radical-generating agent without an adhesive treatment of the resin member.

2. A composite according to claim 1, wherein the thermoplastic resin comprises at least one thermoplastic resin selected from the group consisting of a polyamide-series resin, a polyester-series resin, a poly(thio)ether-series resin, a polycarbonate-series resin, a polyimide-series resin, a polysulfone-series resin, a polyolefinic resin, a halogen-containing vinyl-series resin, a polyurethane-series resin, and a thermoplastic elastomer.

3. A composite according to claim 1, wherein the thermoplastic resin comprises at least one member selected from an aliphatic polyamide-series resin, an aromatic polyester-series resin, a polyacetal-series resin, a polyphenylene ether-series resin, a polysulfide-series resin, a polyether ketone-series resin, an aromatic polycarbonate-series resin, a polyimide-series resin, a polysulfone-series resin, a polyolefinic resin, a halogen-containing vinyl-series resin, a polyurethane-series resin, a polyamide-series elastomer, a polyester-series elastomer, a polyurethane-series elastomer, a polystyrenic elastomer, and a polyolefinic elastomer.

4. A composite according to claim 1, wherein the thermoplastic resin is a thermoplastic resin having at least 2 atoms, as average, selected from a hydrogen atom and a sulfur atom per molecule, each atom having an orbital interaction energy coefficient S of not less than 0.006,

wherein the orbital interaction energy coefficient S is represented by the following formula (1):

S=(C_HOMO,n)²/|E_c−

E_HOMO,n|+(C_LUMO,n)²|E_c−

E_LUMO,n| 

 

(1)

wherein each of E_c, C_HOMO,n, E_HOMO,n, C_LUMO,n, and E_LUMO,n represents a value calculated by a semiempirical molecular orbital method MOPACPM3, E_c representing an orbital energy (eV) of a radical of the radical-generating agent, C_HOMO,n representing a molecular-orbital coefficient of a highest occupied molecular orbital (HOMO) of an n-th hydrogen or sulfur atom constituting a constitutive unit of the thermoplastic resin, E_HOMO,n representing an orbital energy (eV) of the HOMO, C_LUMO,n representing a molecular-orbital coefficient of a lowest unoccupied molecular orbital (LUMO) of the n-th hydrogen or sulfur atom constituting the constitutive unit of the thermoplastic resin, and E_LUMO,n representing an orbital energy (eV) of the LUMO.

5. A composite according to claim 1, wherein at least one component selected from the unvulcanized silicone rubber and the thermoplastic resin comprises a vulcanization-activating agent containing a polyfunctional polymerizable compound having a plurality of polymerizable groups.

6. A composite according to claim 1, wherein the thermoplastic resin comprises a vulcanization-activating agent containing a polyfunctional polymerizable compound having a plurality of polymerizable groups.

7. A composite according to claim 1, wherein at least one component selected from the unvulcanized silicone rubber and the thermoplastic resin comprises a vulcanizing auxiliary comprising a compound having at least 2 hydrogen atoms on average per molecule, each hydrogen atom having an orbital interaction energy coefficient S recited in claim 1 of not less than 0.006.

8. A composite according to claim 1, wherein the vulcanized silicone rubber member is vulcanized or crosslinked with a radical-generating agent and a polyfunctional polymerizable compound having a plurality of polymerizable groups.

9. A composite according to claim 1, wherein the unvulcanized silicone rubber has unsaturated bonds of not less than 2 on average per molecule.

10. A composite according to claim 1, wherein the unvulcanized silicone rubber comprises a silica as a filler.

11. A composite according to claim 10, wherein the silica comprises a dry silica.

12. A composite according to claim 1, wherein the unvulcanized silicone rubber comprises any silicone rubber of the followings (i) to (iii);

(i) a silicone rubber comprising a vulcanization-activating agent containing a polyfunctional polymerizable compound having a plurality of polymerizable groups, and having unsaturated bonds of not less than 2 on average per molecule,

(ii) a silicone rubber comprising a silica and having unsaturated bonds of not less than 2 on the average per molecule, and

(iii) a silicone rubber comprising a vulcanization-activating agent containing a polyfunctional polymerizable compound having a plurality of polymerizable groups, and a silica.

13. A composite according to claim 1, wherein the radical-generating agent comprises an organic peroxide.

14. A composite according to claim 1, wherein the ratio of the radical-generating agent is 1 to 10 parts by weight relative to 100 parts by weight of the unvulcanized rubber.

15. A composite according to claim 5, wherein the ratio of the polyfunctional polymerizable compound is 0.1 to 10 parts by weight relative to 100 parts by weight of at least one component selected from the unvulcanized rubber and the thermoplastic resin.

16. A composite according to claim 7, wherein the ratio of the vulcanization auxiliary is 0.1 to 30 parts by weight relative to 100 parts by weight of at least one component selected from the unvulcanized rubber and the thermoplastic resin.

19. A process according to claim 17, wherein at least one component selected from the unvulcanized silicone rubber and the thermoplastic resin further comprises a vulcanization auxiliary comprising a compound having at least 2 hydrogen atoms on the average per molecule, each hydrogen atom having an orbital interaction energy coefficient S recited in claim 1 of not less than 0.006.

21. A process according to claim 17, which comprises heat-molding the resin member and the vulcanized rubber member with interposing

a vulcanization-activating agent comprising a polymerizable compound having a plurality of polymerizable groups and

a coating agent comprising a vulcanization auxiliary composed of a compound having at least average 2 hydrogen atoms per molecule, each hydrogen atom having an orbital interaction energy coefficient S recited in claim 1 of not less than 0.006

on a contact surface between the resin molding element and the rubber molding element to produce a composite of the resin member bonded to the rubber member.

23. A process for producing a composite, which comprises heat-molding a resin member composed of a thermoplastic resin and a vulcanized rubber member with interposing a coating agent composed of

a vulcanization-activating agent comprising a polymerizable compound having a plurality of polymerizable groups and

a vulcanization auxiliary comprising a compound having at least 2 hydrogen atoms on the average per molecule, each hydrogen atom having an orbital interaction energy coefficient S recited in claim 1 of not less than 0.006

on a contact surface between the resin member and the vulcanized silicone rubber member to produce a composite of the resin member bonds to the rubber member.

17. A process for producing a composite of a thermoplastic resin-containing resin member bonded to a vulcanized silicone rubber member formed by vulcanization of a rubber composition comprising a radical-generating agent and an unvulcanized silicone rubber, which comprises molding a resin molding element and a rubber molding element with contacting said elements each other, and vulcanizing or crosslinking the rubber molding element,

wherein said resin molding element is either of a resin composition and a resin member, each comprising the thermoplastic resin, and

said rubber molding element is either of a rubber composition and a rubber premolded article, each comprising at least an unvulcanized rubber and a radical-generating agent being activating on a surface to be contacted with said resin molding element.

18. A process according to claim 17, wherein at least one component selected from the unvulcanized silicone rubber and the thermoplastic resin further comprises a vulcanization-activating agent containing a polymerizable compound having a plurality of polymerizable groups.

20. A process according to claim 17, which comprises heat-molding the resin member and the vulcanized rubber member with interposing a vulcanization-activating agent comprising a polymerizable compound having a plurality of polymerizable groups on a contact surface between the resin molding element and the rubber molding element to produce a composite the resin member bonded to a rubber member.

22. A process for producing a composite, which comprises heat-molding a resin member composed of a thermoplastic resin and a vulcanized rubber member with interposing a vulcanization-activating agent comprising a polymerizable compound having a plurality of polymerizable groups on a contact surface between the resin member and the vulcanized silicone rubber member to produce a composite of the resin member bonded to the rubber member.