Gas-and-oil impermeable hose construction

• US 5,362,530 A
• Filed: 12/09/1993
• Issued: 11/08/1994
• Est. Priority Date: 09/26/1990
• Status: Expired due to Fees

• Current Assignee: Yokohama Rubber Company Limited
• Original Assignee: Yokohama Rubber Company Limited
• Inventors: Mito, Jun, Ozawa, Osamu, Kitami, Tetsu
• Primary Examiner(s): Robinson, Ellis P.
• Assistant Examiner(s): Speer, Timothy M.
• Application Number:
  US08/163,733
• Time in Patent Office: 334 Days
• Field of Search: 428/35.3, 428/35.4, 428/35.8, 428/36.2, 428/36.7, 428/36.8, 428/36.91, 428/461, 428/465, 428/458, 428/474.9, 428/475.2, 428/483, 428/494, 428/518, 428/522, 138/126, 138/127, 138/133, 138/146, 138/141, 138/143
• US Class Current: 428/36.2
• CPC Class Codes: B32B 1/08 Tubular products
• CPC Class Codes: B32B 15/02 Layer formed of wires, e.g. mesh
• CPC Class Codes: B32B 15/082 comprising vinyl resins; comprising acrylic resins
• CPC Class Codes: B32B 15/085 comprising polyolefins
• CPC Class Codes: B32B 2262/0269 Aromatic polyamide fibres
• CPC Class Codes: B32B 2262/0276 Polyester fibres
• CPC Class Codes: B32B 2262/04 Cellulosic plastic fibres, e.g. rayon
• CPC Class Codes: B32B 2262/103 Metal fibres
• CPC Class Codes: B32B 2305/72 Cured, e.g. vulcanised, cross-linked
• CPC Class Codes: B32B 2307/7246 Water vapor barrier
• CPC Class Codes: B32B 2311/00 Metals, their alloys or their compounds
• CPC Class Codes: B32B 2319/00 Synthetic rubber natural rubber B32B2317/22
• CPC Class Codes: B32B 2323/04 Polyethylene
• CPC Class Codes: B32B 2323/10 Polypropylene
• CPC Class Codes: B32B 2323/16 EPDM, i.e. ethylene propylene diene monomer
• CPC Class Codes: B32B 2367/00 Polyesters, e.g. PET, i.e. polyethylene terephthalate
• CPC Class Codes: B32B 2377/00 Polyamides
• CPC Class Codes: B32B 25/08 of synthetic resin
• CPC Class Codes: B32B 25/18 comprising butyl or halobutyl rubber
• CPC Class Codes: B32B 2597/00 Tubular articles, e.g. hoses, pipes
• CPC Class Codes: B32B 27/08 : of synthetic resin
• CPC Class Codes: B32B 27/12 : next to a fibrous or filamentary layer
• CPC Class Codes: B32B 27/32 : comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/34 : comprising polyamides
• CPC Class Codes: B32B 27/36 : comprising polyesters
• CPC Class Codes: B32B 7/12 : using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: F16L 11/12 : with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting F16L11/11 takes precedence
• CPC Class Codes: F16L 2011/047 : with a diffusion barrier layer
• CPC Class Codes: Y10T 428/1338 : Elemental metal containing
• CPC Class Codes: Y10T 428/1355 : Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
• CPC Class Codes: Y10T 428/1366 : Textile, fabric, cloth, or pile is sandwiched between two distinct layers of material unlike the textile, fabric, cloth, or pile layer
• CPC Class Codes: Y10T 428/1386 : Natural or synthetic rubber or rubber-like compound containing
• CPC Class Codes: Y10T 428/1393 : Multilayer [continuous layer]
• CPC Class Codes: Y10T 428/31681 : Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
• CPC Class Codes: Y10T 428/31692 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31707 : Next to natural rubber
• CPC Class Codes: Y10T 428/31732 : At least one layer is nylon type
• CPC Class Codes: Y10T 428/31736 : Next to polyester
• CPC Class Codes: Y10T 428/31797 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31833 : Next to aldehyde or ketone condensation product or addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31935 : Ester, halide or nitrile of addition polymer

Abstract

A composite hose is disclosed which is constructed essentially with an inner tube and an outer cover, the inner tube being formed from a composition comprised of a specified polymer alloy of a selected class of polyamide resins and acrylic rubbers and the outer cover from a composition comprised of a specified thermoplastic elastomer of a selected class of polyolefin resins and ethylene-propylene-diene rubbers and butyl-based rubber. Impermeability is greatly improved with respect to refrigerant gases and fuel oils.

Claims

1. A highly gas-impermeable, moisture-proof, flexible hose comprising:

(a) an inner tube formed from a first composition comprised of a graft polymer alloy having a continuous phase constituted of at least one polyamide resin, and a disperse phase composed of an acrylic rubber, said one polyamide resin having been grafted with said acrylic rubber;

(b) a reinforcing layer disposed over the inner tube and formed of a synthetic fibrous material or a metallic wiry material; and

(c) an outer cover laminated around the reinforcing layer and formed from a second composition comprised of a thermoplastic elastomer having (a) a continuous phase constituted of a polyolefin resin, and (b) a disperse phase composed of at least one of an ethylene-propylene-diene rubber and a butyl-based rubber, said one rubber having been subjected to vulcanization.

2. The hose according to claim 1 wherein said one polyamide resin in the first composition is nylon 6, nylon 8, nylon 10, nylon 11, nylon 12, nylon 66, nylon 6-nylon 66, nylon 6-nylon 12, nylon 12-nylon 12 or nylon 6-nylon 66-nylon 610 either alone or in combination.

3. The hose according to claim 1 wherein said acrylic rubber in the first composition is a copolymer of an alkyl acrylate ester with a crosslinkable monomer not rich in chlorine, a copolymer of an alkyl acrylate ester with acrylonitrile, a copolymer of an alkyl acrylate ester with an active chlorine-containing monomer, a copolymer of an alkyl acrylate ester with a carboxylic group-containing monomer or a copolymer of an alkyl acrylate ester with an epoxy group-containing monomer.

4. The hose according to claim 1 wherein said polyolefin resin in the second composition is polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-4-methyl-1-pentene or poly-5-methyl-1-hexene or a combination thereof.

5. The hose according to claim 1 wherein said ethylene-propylene-diene rubber in the second composition contains as a diene component dicyclopentadiene, ethylidene norbornene or 1,4-hexadiene.

6. The hose according to claim 1 wherein said butyl-based rubber in the second composition is butyl rubber, chlorinated butyl rubber or brominated butyl rubber.

7. The hose according to claim 1 wherein said synthetic fibrous material is a vinylon, polyester, nylon, rayon or aromatic polyamide fiber, and said metallic wiry material is a steel wire.

21. The hose according to claim 1, wherein said hose is formed without vulcanization.

8. A highly gas impermeable moisture-proof, flexible hose comprising:

(a) an inner tube including an inner peripheral wall and an outer peripheral wall, the inner peripheral wall being formed from a third composition comprised of at least one polyamide resin or a blend thereof with a polyolefin resin, the outer peripheral wall being formed from a first composition comprised of a graft polymer alloy having a continuous phase constituted of at least one polyamide resin, and a disperse phase composed of an acrylic rubber, said one polyamide resin having been grafted with said acrylic rubber, or from a fourth composition comprised of a thermoplastic elastomer having a continuous phase constituted of a polyolefin resin, and a disperse phase made up of at least one rubber selected from the group consisting of an ethylene-propylene-diene rubber, a butyl-based rubber and an acrylonitrile-butadiene rubber, said one rubber having been subjected to vulcanization;

(b) a reinforcing layer disposed over the outer peripheral wall and formed of a synthetic fibrous material or a metallic wiry material; and

(c) an outer cover laminated around the reinforcing layer and formed from a second composition of a thermoplastic elastomer having a continuous phase constituted of a polyolefin resin and a disperse phase composed of at least one of an ethylene-propylene-diene rubber and a butyl-based rubber, said one rubber having been subjected to vulcanization.

9. The hose according to claim 8 wherein said one polyamide resin in the third composition is nylon 6, nylon 8, nylon 10, nylon 11, nylon 12, nylon 66, nylon 6-nylon 66, nylon 6-nylon 12, nylon 12-nylon 12 or nylon 6-nylon 66-nylon 610 either alone or in combination.

10. The hose according to claim 8 wherein said blend in the third composition comprises either one or both of nylon 11 and nylon 12, either one or both of nylon 6 and nylon-6-nylon 66 and a polyolefin resin.

11. The hose according to claim 10 wherein said polyolefin resin is an ethylene or propylene homopolymer, an ethylene-propylene copolymer or a derivative thereof obtainable from reaction with maleic acid.

12. The hose according to claim 8 wherein said one polyamide resin in the first composition is nylon 6, nylon 8, nylon 10, nylon 11, nylon 12, nylon 66, nylon 6-nylon 66, nylon 6-nylon 12, nylon 12-nylon 12 or nylon 6-nylon 66-nylon 610 either alone or in combination.

13. The hose according to claim 8 wherein said acrylic rubber in the first composition is a copolymer of an alkyl acrylate ester with a crosslinkable monomer not rich in chlorine, a copolymer of an alkyl acrylate ester with arylonitrile, a copolymer of an alkyl acrylate ester with an active chlorine-containing monomer, a copolymer of an alkyl acrylate ester with a carboxylic group-containing monomer or a copolymer of an alkyl acrylate ester with an epoxy group-containing monomer.

14. The hose according to claim 8 wherein said polyolefin in the fourth composition is polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-4-methyl-1-pentene or poly-5-methyl-1-hexene or a combination thereof.

15. The hose according to claim 8 wherein said ethylene-propylene-diene rubber in the fourth composition contains as a diene component dicyclopentadiene, ethylidene norbornene or 1,4-hexadiene.

16. The hose according to claim 8 wherein said butyl-based rubber in the fourth composition is butyl rubber, chlorinated butyl rubber or brominated butyl rubber.

17. The hose according to claim 8 wherein said polyolefin resin in the second composition is polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-4-methyl-1-pentene or poly-5-methyl-1-hexene or a combination thereof.

18. The hose according to claim 8 wherein said ethylene-propylene-diene rubber in the second composition contains as a diene component dicyclopentadiene, ethylidene norbornene or 1,4-hexadiene.

19. The hose according to claim 8 wherein said butyl-based rubber in the second composition is butyl rubber, chlorinated butyl rubber or brominated butyl rubber.

20. The hose according to claim 8 wherein said synthetic fibrous material is a vinylon, polyester, nylon, rayon or aromatic polyamide fiber, and said metallic wiry material is a steel wire.

22. The hose according to claim 8, wherein said hose is formed without vulcanization.

23. A highly gas-impermeable, moisture-proof, flexible hose comprising:

(a) an inner tube including an inner peripheral wall and an outer peripheral wall, the inner peripheral wall being formed from a first composition comprised of a graft polymer alloy having a continuous phase constituted of at least one polyamide resin and a disperse phase composed of an acrylic rubber, said one polyamide resin having been grafted with said acrylic rubber, the outer peripheral wall being formed from a fourth composition comprised of a thermoplastic elastomer having a continuous phase constituted of a polyolefin resin and a disperse phase made up of at least one rubber selected from the group consisting of an ethylene-propylene-diene rubber, a butyl-based rubber and an acrylonitrile-butadiene rubber, said one rubber having been subjected to vulcanization;

(b) a reinforcing layer disposed over the outer peripheral wall and formed of a synthetic fibrous material or a metallic wiry material; and

(c) an outer cover laminated around the reinforcing layer and formed from a second composition of a thermoplastic elastomer having a continuous phase constituted of a polyolefin resin and a disperse phase composed of at least one of an ethylene-propylene-diene rubber and a butyl-based rubber, said one rubber having been subjected to vulcanization.

24. The hose according to claim 23 wherein said one polyamide resin in the first composition is nylon 6, nylon 8, nylon 10, nylon 11, nylon 12, nylon 66, nylon 6-nylon 66-nylon 610 either alone or in combination.

25. The hose according to claim 23 wherein said acrylic rubber in the first composition is a copolymer of an alkyl acrylate ester with a crosslinkable monomer not rich in chlorine, a copolymer of an alkyl acrylate ester with acrylonitrile, a copolymer of an alkyl acrylate ester with an active chlorine-containing monomer, a copolymer of an alkyl acrylate ester with a carboxylic group-containing monomer or a copolymer of an alkyl acrylate ester with an epoxy group-containing monomer.

26. The hose according to claim 23 wherein said polyolefin in the fourth composition is polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-4-methyl-1-pentene or poly-5-methyl-1-hexene or a combination thereof.

27. The hose according to claim 23 wherein said ethylene-propylene-diene rubber in the fourth composition contains as a diene component dicyclopentadiene, ethylidene norbornene or 1,4-hexadiene.

28. The hose according to claim 23 wherein said butyl-based rubber in the fourth composition is butyl rubber, chlorinated butyl rubber or brominated butyl rubber.

29. The hose according to claim 23 wherein said polyolefin resin in the second composition is polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-4-methyl-1-pentene or poly-5-methyl-1-hexene or a combination thereof.

30. The hose according to claim 23 wherein said ethylene-propylene-diene rubber in the second composition contains as a diene component dicyclopentadiene, ethylidene norbornene or 1,4-hexadiene.

31. The hose according to claim 23 wherein said butyl-based rubber in the second composition is butyl rubber, chlorinated butyl rubber or brominated butyl rubber.

32. The hose according to claim 23 wherein said synthetic fibrous material is a vinylon, polyester, nylon, rayon or aromatic polyamide fiber, and said metallic wiry material is a steel wire.

33. The hose according to claim 23 wherein said hose is formed without vulcanization.