WO2010073375A1 - 冷媒輸送用ホース - Google Patents
冷媒輸送用ホース Download PDFInfo
- Publication number
- WO2010073375A1 WO2010073375A1 PCT/JP2008/073747 JP2008073747W WO2010073375A1 WO 2010073375 A1 WO2010073375 A1 WO 2010073375A1 JP 2008073747 W JP2008073747 W JP 2008073747W WO 2010073375 A1 WO2010073375 A1 WO 2010073375A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- layer
- polyamide
- mass
- hose
- Prior art date
Links
- 239000003507 refrigerant Substances 0.000 title claims abstract description 27
- 239000010410 layer Substances 0.000 claims abstract description 151
- 229920001971 elastomer Polymers 0.000 claims abstract description 134
- 239000005060 rubber Substances 0.000 claims abstract description 134
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000004952 Polyamide Substances 0.000 claims abstract description 32
- 229920002647 polyamide Polymers 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000006229 carbon black Substances 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 15
- 229920005555 halobutyl Polymers 0.000 claims abstract description 15
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 14
- 229920000098 polyolefin Polymers 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000012790 adhesive layer Substances 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims description 47
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229920000571 Nylon 11 Polymers 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 26
- 230000001070 adhesive effect Effects 0.000 abstract description 26
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000001464 adherent effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 49
- 230000000052 comparative effect Effects 0.000 description 21
- 230000032798 delamination Effects 0.000 description 19
- 238000004073 vulcanization Methods 0.000 description 16
- 230000003014 reinforcing effect Effects 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- -1 ethylene, propylene Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000004957 Zytel Substances 0.000 description 6
- 229920006102 Zytel® Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000014692 zinc oxide Nutrition 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
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- 239000000654 additive Substances 0.000 description 4
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- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920005556 chlorobutyl Polymers 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 241000375392 Tana Species 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000006237 Intermediate SAF Substances 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
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- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PKMTWMDBJHRDBM-ODZAUARKSA-N (z)-but-2-enedioic acid;zinc Chemical compound [Zn].OC(=O)\C=C/C(O)=O PKMTWMDBJHRDBM-ODZAUARKSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 239000004902 Softening Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
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- 238000009954 braiding Methods 0.000 description 1
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- 125000001246 bromo group Chemical group Br* 0.000 description 1
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- 230000006835 compression Effects 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
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- 229920006324 polyoxymethylene Polymers 0.000 description 1
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- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- WDHVIZKSFZNHJB-UHFFFAOYSA-L zinc;butanoate Chemical compound [Zn+2].CCCC([O-])=O.CCCC([O-])=O WDHVIZKSFZNHJB-UHFFFAOYSA-L 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
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- F16L11/20—Double-walled hoses, i.e. two concentric hoses
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
- F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer
Definitions
- the present invention relates to a refrigerant transport hose.
- Patent Document 1 describes a refrigerant transport hose in which a gas barrier layer and a rubber layer formed of a specific rubber composition are bonded with an adhesive.
- Patent Documents 2 and 3 have proposed a hose in which a resin and rubber are joined without using an adhesive or the like.
- an object of the present invention is to provide a hose in which a gas barrier layer and a rubber layer are joined without using an adhesive or the like, and further, durability is significantly higher than that of the conventional one.
- the present inventor has intensively studied and a refrigerant transport hose comprising an inner tube layer composed of a gas barrier layer and a rubber layer, containing a specific component in a specific quantitative ratio, is formed without using an adhesive or the like. Has been found to be strongly bonded and have significantly superior durability compared to the prior art, thus completing the present invention.
- the present invention includes the following (1) to (3).
- a refrigerant transport hose comprising an inner tube layer comprising a gas barrier layer and a rubber layer in close contact with the outer surface thereof, wherein the gas barrier layer is obtained by blending a polyamide and a carboxyl group-containing modified polyolefin.
- the rubber layer is made of a rubber composition comprising 100 parts by mass of raw rubber, an alkylphenol formaldehyde resin: 1 to 15 parts by mass, and carbon black: 30 to 80 parts by mass
- the raw rubber is composed of BIMS, a copolymer rubber which is butyl rubber and / or halogenated butyl rubber, and EPDM, the content of the BIMS in the raw rubber is 5 to 40 parts by mass, and the BIMS and the copolymer
- the total content with rubber is 20 to 80 parts by mass, and the EPDM content is 80 to 20 parts by mass.
- the refrigerant transport hose according to (1) wherein the copolymer rubber is a halogenated butyl rubber.
- the polyamide is polyamide 6, polyamide 11, polyamide 12, polyamide 4-6, polyamide 6-6, polyamide 6-10, polyamide 6-12 and polyamide MXD-6, and a copolymer of two or more thereof.
- the hose for transporting refrigerant according to the above (1) or (2) which is at least one selected from the group consisting of:
- the present invention it is possible to provide a hose in which the gas barrier layer and the rubber layer are bonded without using an adhesive or the like, and the durability is much superior to the conventional one.
- FIG. 1 is a perspective view of a preferred embodiment of the hose of the present invention.
- the hose of the present invention will be described in detail.
- the hose of the present invention is a refrigerant transport hose comprising an inner tube layer composed of a gas barrier layer and a rubber layer in close contact with the outer surface thereof. There is no adhesive layer between the gas barrier layer and the rubber layer.
- the hose of the present invention is included even in the case where the inner tube layer only is formed and no other layer is formed.
- the configuration of the hose of the present invention will be described later using a specific example, but may be the same as the conventional one.
- the gas barrier layer in the hose of the present invention comprises a modified polyamide obtained by blending a polyamide and a carboxyl group-containing modified polyolefin.
- the gas barrier layer should just consist of the said modified polyamide, and may contain another component (for example, additive etc.) in the range which can achieve the objective of this invention. Thus, even if it contains other components, it is within the scope of the present invention.
- polyamide is not particularly limited, it is composed of polyamide 6, polyamide 11, polyamide 12, polyamide 4-6, polyamide 6-6, polyamide 6-10, polyamide 6-12 and polyamide MXD-6, and a copolymer of two or more thereof. It is preferably at least one selected from the group.
- carboxyl group-containing modified polyolefin examples include a functional group of about 0.1 by graft polymerization of an acid anhydride such as maleic anhydride to a polyolefin obtained by homopolymerizing or copolymerizing an olefin such as ethylene, propylene or butadiene, or a diene monomer.
- a modified polyolefin introduced with ⁇ 10 mol% is preferably used.
- the blend ratio (mass ratio) of the polyamide and the carboxyl group-containing modified polyolefin is preferably 90/10 to 50/50, more preferably 85/15 to 65/35.
- Increasing the proportion of the carboxyl group-containing modified polyolefin improves the flexibility of the hose of the present invention, but the refrigerant permeation resistance may decrease, and if it decreases, the refrigerant permeation resistance improves, but the adhesion to the rubber layer and flexibility Tend to be inferior.
- modified polyamide examples include a Zytel ST series such as Zytel ST801, Zytel ST811, and Zytel ST811HS manufactured by DuPont, which is considered to be an alloy of polyamide 6 and maleic anhydride-modified polyolefin.
- the gas barrier layer can be formed by extruding the modified polyamide into a tubular shape, for example.
- the thickness of the gas barrier layer is not particularly limited, but is preferably 0.01 to 0.50 mm, more preferably 0.05 to 0.30 mm, and even more preferably 0.05 to 0.20 mm. Within such a range, molding workability, refrigerant permeation resistance, and flexibility tend to be better.
- the rubber layer is made of a rubber composition obtained by blending a specific amount of an alkylphenol formaldehyde resin and a specific amount of carbon black into a raw rubber.
- the rubber layer only needs to be made of raw rubber, an alkylphenol formaldehyde resin, and carbon black, and may contain other components as long as the object of the present invention can be achieved. Thus, even if it contains other components, it is within the scope of the present invention.
- the raw rubber is composed of BIMS, copolymer rubber which is butyl rubber and / or halogenated butyl rubber, and EPDM.
- BIMS contained in the raw rubber
- BIMS has a p-alkylstyrene (PAS) content of 5 to 25% by mass and a bromine (Br) content of 1.5% by mass or more, and the mass ratio of p-alkylstyrene units to bromine units is 0.00.
- PAS p-alkylstyrene
- Br bromine
- This is a bromide of a copolymer rubber of an isomonoolefin having 4 to 7 carbon atoms and p-alkylstyrene, wherein 15 ⁇ Br / PAS ⁇ 0.40.
- the Mooney viscosity (ML1 + 8, 125 ° C.) is 30 or more.
- Examples of the isomonoolefin having 4 to 7 carbon atoms include isobutylene.
- Examples of p-alkylstyrene include styrene having an alkyl group having 1 to 5 carbon atoms in the para position, such as p-methylstyrene and p-ethylstyrene.
- the content of p-alkylstyrene in BIMS is 5 to 25% by mass, preferably 5 to 10% by mass, for all those having a p-alkylstyrene skeleton including brominated products of alkyl groups of p-alkylstyrene. .
- When it is 25% by mass or less, the rubber composition does not become brittle at a low temperature and is excellent in cold resistance.
- BIMS has a commercial item, for example, EXXPRO series made by Exxon Chemical.
- Exxpro 3745 manufactured by the same company which is a bromide of a copolymer rubber of isobutylene and p-methylstyrene, can be mentioned.
- the copolymer rubber contained in the raw rubber will be described.
- the copolymer rubber is butyl rubber and / or halogenated butyl rubber, and is preferably halogenated butyl rubber. This is because the durability of the hose obtained according to the present invention is further increased.
- the butyl rubber general isobutylene / isoprene rubber can be used, and is not particularly limited, but the content of isoprene is 0.6 to 2.5 mol% as the degree of unsaturation, and the molecular weight is 35 to 60 (125 in Mooney viscosity). ° C).
- Examples of the halogenated butyl rubber include chlorinated butyl rubber and brominated butyl rubber.
- halogenated butyl rubbers can also be general ones.
- the chlorine content is 1 to 2.5% by mass
- the isoprene content is 0.6 to 0.6 as the degree of unsaturation. It is preferably 2.5 mol% and the molecular weight is 30 to 60 (125 ° C.) in Mooney viscosity.
- the bromine content is 1 to 2.5 mass%
- the isoprene content is 0.6 to 2.5 mol% as the degree of unsaturation
- the molecular weight is 25 to 55 (125 ° C.) in Mooney viscosity. ) Is preferable.
- the EPDM contained in the raw rubber is not particularly limited as long as it is a general copolymer rubber made of ethylene, propylene and diene.
- An example of a commercially available product is Mitsui EPT 4070 manufactured by Mitsui Chemicals.
- the propylene content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.
- Examples of the diene component include ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene. Among these, ethylidene norbornene having a high crosslinking rate is preferable.
- the amount of the diene component is preferably from 3 to 25 in terms of iodine value, and more preferably from 5 to 20.
- the content of the BIMS in the raw rubber is 5 to 40 parts by mass, and the total content of the BIMS and the copolymer rubber which is a butyl rubber and / or a halogenated butyl rubber is 20 to 80 parts by mass.
- the content of is 80 to 20 parts by mass.
- the content of BIMS is less than 5 parts by mass, it is difficult to obtain the required rubber attachment. That is, it becomes difficult to form the adhesive rubber layer with a necessary thickness on the surface of the gas barrier layer. Moreover, when it exceeds 40 mass parts, the required adhesive force will be hard to be obtained. That is, it becomes difficult to firmly adhere the rubber layer to the surface of the gas barrier layer.
- the abundance ratio of the above EPDM is preferably 70 to 50 parts by mass. Moreover, if the abundance ratio of EPDM is less than 20 parts by mass, it is difficult to obtain the required adhesive strength and rubber attachment. Moreover, when it exceeds 80 mass parts, a vulcanization
- the alkylphenol formaldehyde resin can act as a vulcanizing agent for the raw rubber.
- the alkylphenol formaldehyde resin also includes a halogenated alkylphenol formaldehyde resin (halogenated alkylphenol formaldehyde resin). Of these, brominated alkylphenol formaldehyde resins are preferred.
- a commercially available product such as Takiroll 250-1 manufactured by Taoka Chemical Co., Ltd. can be used as Takiroll 250-1 manufactured by Taoka Chemical Co., Ltd. can be used.
- the compounding amount of the alkylphenol formaldehyde resin is 1 to 15 parts by mass, preferably 2 to 10 parts by mass, and more preferably 2 to 7 parts by mass with respect to 100 parts by mass of the raw rubber. If it is less than 1 part by mass, it may be difficult to obtain the required adhesive strength. That is, it may be difficult to firmly adhere the rubber layer to the surface of the gas barrier layer. Moreover, when it exceeds 15 mass parts, the physical property (hardness) of a rubber layer may be impaired.
- N 2 SA Colloidal properties of carbon black used in the present invention are N 2 SA ⁇ 75m 2 / g , and DBP oil absorption ⁇ 90cm 3 / 100g.
- N 2 SA is 75 m 2 / g or less than DBP absorption is less than 90cm 3/100 g, it is difficult to firmly bond the rubber layer on the surface of the gas barrier layer.
- N 2 SA is preferably 80 to 150 m 2 / g, and more preferably 80 to 120 m 2 / g.
- DBP oil absorption amount is 95 ⁇ 140cm 3 / 100g, and more preferably 100 ⁇ 130cm 3 / 100g.
- N 2 SA means the molecular weight of nitrogen adsorbed on the surface of carbon black, and specifically means a value obtained by measurement by a method prescribed in JIS K 6217-2.
- the DBP oil absorption amount means the amount of oil absorbed by the carbon black aggregate, and specifically means the value obtained by measurement by the method specified in JIS K 6217-4.
- the compounding amount of the carbon black is 30 to 80 parts by mass, preferably 40 to 65 parts by mass with respect to 100 parts by mass of the raw rubber. If it is less than 30 parts by mass, it is difficult to obtain the required adhesive force. That is, it becomes difficult to firmly adhere the rubber layer to the surface of the gas barrier layer. On the other hand, when the amount exceeds 80 parts by mass, the viscosity of the unvulcanized rubber becomes high and the workability is impaired.
- the rubber layer may further contain zinc white (ZnO), a vulcanization aid, a vulcanization accelerator, and an additive as other components in addition to the raw rubber, the alkylphenol formaldehyde resin, and the carbon black.
- ZnO zinc white
- a vulcanization aid include fatty acids such as acetyl acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid; zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, Examples include fatty acid zinc such as zinc maleate.
- vulcanization accelerator examples include thiurams such as tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (TETD); aldehydes and ammonia such as hexamethylenetetramine; guanidines such as diphenylguanidine; dibenzothiazyl disulfide; (DM) and the like; sulfenamides such as cyclohexylbenzothiazylsulfenamide and the like.
- the additive include fillers such as clay, softeners such as paraffinic oil, plasticizers, processing aids, antiaging agents, and pigments.
- the method for obtaining a rubber composition obtained by blending the raw rubber, the alkylphenol formaldehyde resin, and the carbon black is not particularly limited.
- a predetermined amount of BIMS, butyl rubber and / or halogenated butyl rubber, and EPDM are mixed with a predetermined amount of carbon black and, if necessary, additives such as paraffinic oil and processing aids, and mixed by a roll, a Banbury mixer, etc.
- the specific amount of the alkylphenol formaldehyde resin and, if necessary, other zinc white, vulcanization aid, and vulcanization accelerator can be added and mixed.
- the thickness of the rubber layer is not particularly limited, but is preferably 0.5 to 3.0 mm.
- the hose of the present invention includes an inner tube layer composed of such a gas barrier layer and a rubber layer closely attached to the outer surface thereof, and is used for transporting a refrigerant that does not have an adhesive layer between the gas barrier layer and the rubber layer.
- a hose If the inner tube layer is not composed of a gas barrier layer and a rubber layer containing the specific components described above in a specific content, the gas barrier layer and the rubber layer are firmly vulcanized and bonded without using an adhesive. It is not possible. That is, high adhesiveness (with high adhesive strength and high rubber) cannot be exhibited.
- the inner diameter, outer diameter, and length of the hose of the present invention are not particularly limited.
- the inner diameter is preferably 5 to 20 mm, and more preferably 7 to 17 mm.
- the hose of the present invention may further have a reinforcing layer and an outer tube layer.
- the reinforcing layer may be formed in a blade shape or a spiral shape, and is not particularly limited.
- the material to be used include a thread and a wire.
- the reinforcing yarn include yarns made of vinylon fiber, rayon fiber, polyester fiber, nylon fiber, aromatic polyamide fiber and the like.
- a hard steel wire is exemplified, and more specifically, a brass plated wire or a galvanized wire is exemplified for rust prevention and adhesion imparting.
- the outer tube layer is formed on the outer side of the inner tube layer or the reinforcing layer, and the material, structure, thickness, etc. thereof are not particularly limited, and generally used rubber compositions, resins, metal wires, etc. Can be used.
- the raw rubber can also be used as the rubber composition. Even if a vulcanizing agent, a filler, a reinforcing agent, a plasticizer, an anti-aging agent, a vulcanization accelerator, a softening agent, a tackifier, a lubricant, a dispersant, a processing aid, and the like are appropriately blended in the rubber composition. Good.
- the resin examples include polyamide resin, polyester resin, polyurethane resin, polyacetal resin, vinyl chloride resin, polypropylene, and polyethylene.
- a metal and a fiber can also be contained for the improvement of the vibration absorption performance and the strength improvement by weight increase.
- the outer tube layer can be, for example, solid or sponge. Further, the outer tube layer may be, for example, a cylindrical type that is used by inserting the hose of the present invention, a spiral type, or a spring type that is wound around the hose of the present invention.
- the thickness of the outer tube layer is preferably 1 to 5 mm, more preferably 0.5 to 3 mm, and even more preferably 1 to 2 mm.
- the outer tube layer may be formed of a plurality of layers.
- FIG. 1 is a view showing a preferred embodiment of the hose of the present invention.
- the hose 1 of the present invention includes an inner tube layer comprising a gas barrier layer 21 and a rubber layer 22 in close contact with the outer surface thereof. There is no adhesive layer between the gas barrier layer 21 and the rubber layer 22, but the two layers are firmly adhered.
- the reinforcing layer 3 is provided on the upper surface of the rubber layer 22, and the outer tube layer 4 is provided on the upper surface thereof.
- the hose of the present invention is not particularly limited as long as it has the inner tube layer, and may have other layers on the outer side of the outer tube layer in the preferred embodiment described with reference to FIG.
- the hose of the present invention does not necessarily have the reinforcing layer as described above, but if the reinforcing layer is provided, the tensile breaking strength of the hose, the usable pressure range, and the fitting property of the hose are improved. preferable.
- the hose of the present invention is used for a high-pressure part, it is preferable to have a reinforcing layer.
- the manufacturing method of the hose of this invention is demonstrated.
- the manufacturing method of the hose of this invention is not specifically limited, A conventionally well-known method can be used.
- the gas barrier layer and the rubber layer can be obtained by extrusion molding.
- the rubber layer can be molded using the rubber composition obtained by the above method.
- a rubber layer is laminated on the outer surface of the gas barrier layer, and a reinforcing layer and then an outer rubber layer are laminated by braiding or spiral winding. Later, it can be obtained by vulcanizing the whole. Vulcanization can be carried out at a temperature of about 150 to 180 ° C.
- a gas barrier layer, a rubber layer, a reinforcing layer and an outer tube layer are laminated in this order on a mandrel, and then these layers are subjected to conditions of 140 to 190 ° C. and 30 to 180 minutes. It can be produced by vulcanization adhesion by press vulcanization, steam vulcanization, oven vulcanization (hot air vulcanization) or hot water vulcanization.
- ⁇ Test 1 Extrusion processability test of rubber composition> The raw materials shown below were mixed in the quantitative ratios (parts by mass) shown in Tables 1 to 3 to obtain rubber compositions in Examples and Comparative Examples. Specifically, carbon black, paraffin oil, and stearic acid are added to BIMS, butyl rubber and / or halogenated butyl rubber, and EPDM, mixed with a roll, a Banbury mixer, etc., and subsequently, alkylphenol formaldehyde resin and ZnO are added. The composition was obtained by mixing.
- Butyl rubber EXXON BUTYL 268, manufactured by Nippon Butyl Co., Ltd.
- Chlorinated butyl rubber Cl-IIR: EXXON CHLOROBUTYL 1066, manufactured by Nihon Butyl Co., Ltd.
- Brominated butyl rubber (Br-IIR): manufactured by EXXON BROMOBUTYL 2255 BIMS: Exxpro 3745, EXXONMOBIL CHEMICAL COMPANY EPDM: Mitsui EPT4070, Mitsui Chemicals carbon black (CB (ISAF)): Show black N220, Showa Cabot carbon black (CB (HAF)): Show black N330, Showa Cabot carbon black (CB (FEF) ): Show Black N550, manufactured by Showa Cabot, Inc.
- Stearic acid Lunac YA, manufactured by Kao Corporation Paraffin oil: Process oil 123, manufactured by Showa Shell Sekiyu Co., Ltd.
- ZnO Zinc oxide, 3 types, Brodinated alkylphenol formaldehyde resin : Tacchi roll 250-1, Taoka Chemical Co., Ltd.
- those represented by the ISAF and HAF can satisfy the N 2 SA ⁇ 75m 2 / g and DBP oil absorption amount ⁇ 90cm 3 / 100g is, does not satisfy those represented by the FEF.
- the minimum Mooney viscosity of each obtained rubber composition was measured.
- the minimum Mooney viscosity means a value (Vm) measured at 125 ° C. in the Mooney scorch test of JIS K 6300-1.
- a round bar-shaped head was assembled in a small screw type extruder (a screw used a compression type), and the extrusion performance was confirmed at a head and cylinder temperature of 80 ° C. and a rotation speed of 60 rpm.
- the shape of the shape that can be used as a hose, such as the appearance, is indicated by “ ⁇ ”, and the shape that is at the unusable level is indicated by “X”.
- Adhesion test> A hose comprising an inner tube layer was produced using the rubber composition and modified polyamide of each Example and each Comparative Example. Specifically, at first, Zytel ST811HS (denoted as “Zytel” in the table) or polyamide resin (denoted as “PA6” in the table) is drawn down onto a mandrel (outer diameter of 11 mm) using an extruder. To form a gas barrier layer having a thickness of 0.1 mm. Next, a rubber layer having a thickness of 1.4 mm was formed on the outer surface of the gas barrier layer obtained above using the obtained rubber composition. After the rubber layer was laminated on the outer surface of the gas barrier layer, the whole was vulcanized.
- Vulcanization was carried out by applying vapor pressure at about 150 to 180 ° C. An inner tube layer having a thickness of 1.5 mm and an outer diameter of 14 mm was obtained.
- the gas barrier layer and the rubber layer were bonded using an adhesive (Chemlok 402X, manufactured by Lord Corporation).
- the adhesive strength and rubber attachment when the rubber layer was peeled off at a peeling speed of 50 mm / min were measured.
- the adhesive force means an adhesive force (N) per 25 mm in width.
- the thing with an adhesive force of 40 N / 25 mm or more was evaluated as “ ⁇ ”, and the adhesive force of less than 40 N / 25 mm was evaluated as “x”.
- the term “with rubber” means the area ratio (%) where the rubber remains without peeling off.
- the thickness of the rubber remaining without being peeled is also measured and indicated by “thick”, “thin”, “interface” (meaning that it is peeled off at the interface between the gas barrier layer and the rubber layer). It was. Then, the thick one was evaluated as “ ⁇ (good)”, the “thin” one as “ ⁇ ”, and the one peeled off at the “interface” as “ ⁇ ”.
- Hose in each Example and each Comparative Example was produced by the same method as in Test 3 above.
- the inner diameter of the hose was 11 mm
- the outer diameter was 18 mm (the thickness of the inner tube layer was 1.5 mm), and the length was 50 cm.
- the refrigerant R-134a
- the refrigerant was sealed so as to be 0.6 g / cm 3 .
- the hose was cut in half (vertically divided), and peeling of the rubber layer (tana drop) was confirmed. A case where no drop has occurred is indicated as “ ⁇ ”, and a case where a drop has occurred is indicated as “X”.
- ⁇ Test 5 Gas permeability test> For each of the hoses in Example 3 and Example 4, four 50 cm long hoses with metal fittings attached to both ends of the hose were prepared. Next, the refrigerant
- coolant was enclosed so that it might become 0.6 g / cm ⁇ 3 > about three of them. The remaining one was sealed without enclosing the refrigerant. Then, by measuring the mass after 24 hours at 100 ° C. and the mass after 96 hours, the gas permeation amount (g / m ⁇ 72h) per 72 hours was calculated, and the permeability of R-134a was examined. .
- Comparative Example 1-1 is an embodiment in which the gas barrier layer and the rubber layer are bonded with an adhesive. In this case, it was found that the rubber attachment became thin, the tana drop occurred in the delamination test, and the adhesion between the gas barrier layer and the rubber layer was insufficient (see Table 1).
- Comparative Examples 1-2 to 5 are examples in which a rubber layer was formed using a composition not containing any one or more of BIMS, butyl rubber and / or halogenated butyl rubber, and EPDM. In these cases, it was found that delamination occurred in the delamination test, and adhesion between the gas barrier layer and the rubber layer was insufficient (see Table 1). Comparative Example 1-2, Comparative Example 2, and Comparative Example 3 correspond to the aspects described in Patent Document 3. Comparative Example 2 also corresponds to the aspect described in Patent Document 2.
- Comparative Examples 6 and 7 are examples in which a rubber layer was formed using a composition having a composition ratio of any one or more of BIMS, butyl rubber and / or halogenated butyl rubber, and EPDM outside the scope of the present invention. In these cases, it was found that delamination occurred in the delamination test and the adhesion between the gas barrier layer and the rubber layer was insufficient (see Table 1).
- Comparative Example 8 carbon black, N 2 SA ⁇ 75m 2 / g, and was used which does not satisfy the DBP absorption ⁇ 90cm 3 / 100g and (FEF), using a composition outside the scope of the present invention
- This is an example in which a rubber layer is formed. In these cases, it was found that delamination occurred in the delamination test and the adhesion between the gas barrier layer and the rubber layer was insufficient (see Table 1).
- Examples 1 to 10 had high adhesive strength, good rubberity, and no delamination occurred in the delamination test.
- the results were particularly good in Examples 3 and 4 (see Table 1).
- the results of the gas permeability test in Example 3 and Example 4 were both 3.3 [g / (m ⁇ 72h)], confirming that it can be preferably applied as a refrigerant transport hose.
- Comparative Example 9 the amount of carbon black added to 100 parts by mass of the raw rubber is 25 parts by mass, which is outside the scope of the present invention. In this case, it was found that the delamination occurred in the delamination test and the adhesion between the gas barrier layer and the rubber layer was insufficient (see Table 2). Further, in Comparative Example 10, the amount of carbon black added to 100 parts by mass of the raw rubber is 85 parts by mass, which is outside the scope of the present invention. In this case, the extrudability was insufficient.
- Examples 11 and 12 had high adhesive strength, good rubber attachment, and no delamination occurred in the delamination test (see Table 2). Moreover, the workability was also good.
- Comparative Example 11 is 0.50 parts by mass of brominated alkylphenol formaldehyde resin with respect to 100 parts by mass of the raw rubber, which is outside the scope of the present invention.
- the comparative example 12 is 18 mass parts of brominated alkylphenol formaldehyde resins with respect to 100 mass parts of raw rubber, and is outside the scope of the present invention. In these cases, it was found that delamination occurred in the delamination test, and adhesion between the gas barrier layer and the rubber layer was insufficient (see Table 2).
- Examples 13 to 15 had high adhesive strength, good rubberity, and no delamination occurred in the delamination test (see Table 2).
- Comparative Examples 13 to 15 are embodiments using PA6 as the gas barrier layer, and are outside the scope of the present invention. In these cases, it was found that the rubber attachment was poor, the tana drop occurred in the delamination test, and the adhesion between the gas barrier layer and the rubber layer was insufficient (see Table 3). Comparative Examples 13 and 14 correspond to the aspects described in Patent Document 1.
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Abstract
Description
そこで、特許文献2および3では、接着剤等を使用せずに樹脂とゴムとを接合したホースが提案された。
したがって本発明の目的は、接着剤等を用いずにガスバリア層とゴム層とが接合されており、さらに従来と比較して耐久性が格段に優れたホースを提供することにある。
(1)ガスバリア層とその外表面に密着したゴム層とからなる内管層を備える冷媒輸送用ホースであって、前記ガスバリア層が、ポリアミドとカルボキシル基含有変性ポリオレフィンとをブレンドして得られる変性ポリアミドからなり、前記ゴム層が、原料ゴム:100質量部に対して、アルキルフェノールホルムアルデヒド樹脂:1~15質量部、およびカーボンブラック:30~80質量部を配合してなるゴム組成物からなり、前記原料ゴムが、BIMSと、ブチルゴムおよび/またはハロゲン化ブチルゴムである共重合ゴムと、EPDMとからなり、前記原料ゴムにおける前記BIMSの含有量が5~40質量部であり、前記BIMSと前記共重合ゴムとの含有量の合計が20~80質量部であり、EPDMの含有量が80~20質量部であり、前記カーボンブラックは、N2SA≧75m2/g、かつDBP吸油量≧90cm3/100gであり、前記ガスバリア層と前記ゴム層との間に接着剤層を有さない、冷媒輸送用ホース。
(2)前記共重合ゴムがハロゲン化ブチルゴムである、上記(1)に記載の冷媒輸送用ホース。
(3)前記ポリアミドが、ポリアミド6、ポリアミド11、ポリアミド12、ポリアミド4-6、ポリアミド6-6、ポリアミド6-10、ポリアミド6-12およびポリアミドMXD-6ならびにこれらの中の2種以上のコポリマーからなる群から選ばれる少なくとも1つである、上記(1)または(2)に記載の冷媒輸送用ホース。
2 内管層
21 ガスバリア層
22 ゴム層
3 補強層
4 外管層
本発明のホースは、ガスバリア層とその外表面に密着したゴム層とからなる内管層を備える冷媒輸送用ホースである。このガスバリア層とゴム層との間には接着剤からなる層は存在しない。前記内管層のみからなり他の層を有さない場合でも本発明のホースに含まれる。
本発明のホースの構成は後に具体例を用いて説明するが、従来のものと同様であってよい。
ガスバリア層について説明する。
本発明のホースにおけるガスバリア層は、ポリアミドとカルボキシル基含有変性ポリオレフィンとをブレンドして得られる変性ポリアミドからなる。
なお、ガスバリア層は前記変性ポリアミドからなっていればよく、本発明の目的を達成できる範囲で他の成分(例えば添加剤等)を含んでもよい。このように他の成分を含んでいる場合であっても、本発明の範囲内である。
ガスバリア層の厚さは特に限定されないものの、0.01~0.50mmが好ましく、0.05~0.30mmがより好ましく、0.05~0.20mmがさらに好ましい。このような範囲であると、成形作業性および耐冷媒透過性ならびに可撓性がより良好となる傾向がある。
ゴム層について説明する。
ゴム層は、原料ゴムに特定量のアルキルフェノールホルムアルデヒド樹脂と、特定量のカーボンブラックを配合してなるゴム組成物からなる。
ここで、ゴム層は原料ゴムとアルキルフェノールホルムアルデヒド樹脂とカーボンブラックとからなっていればよく、本発明の目的を達成できる範囲で他の成分を含んでもよい。このように他の成分を含んでいる場合であっても、本発明の範囲内である。
原料ゴムはBIMSと、ブチルゴムおよび/またはハロゲン化ブチルゴムである共重合ゴムと、EPDMとからなる。
BIMSは、p-アルキルスチレン(PAS)含有量が5~25質量%、臭素(Br)含有量が1.5質量%以上であり、p-アルキルスチレン単位と臭素単位との質量比が0.15≦Br/PAS≦0.40である、炭素原子数4~7のイソモノオレフィンとp-アルキルスチレンとの共重合ゴムの臭素化物である。ムーニー粘度(ML1+8、125℃)は30以上である。
前記共重合ゴムは、ブチルゴムおよび/またはハロゲン化ブチルゴムであり、ハロゲン化ブチルゴムであることが好ましい。得られる本発明のホースの耐久性がより高まるからである。
ブチルゴムとしては、一般的なイソブチレン・イソプレンゴムを使用でき、特に制限されないが、そのイソプレンの含有量は不飽和度として0.6~2.5モル%、分子量はムーニー粘度で35~60(125℃)であることが好ましい。また、ハロゲン化ブチルゴムとしては塩素化ブチルゴム、臭素化ブチルゴム等が挙げられる。これらのハロゲン化ブチルゴムも、一般的なものを使用することができるが、塩素化ブチルゴムの場合、塩素含有量は1~2.5質量%、イソプレンの含有量は不飽和度として0.6~2.5モル%、分子量はムーニー粘度で30~60(125℃)であることが好ましい。また、臭素化ブチルゴムの場合、臭素含有量は1~2.5質量%、イソプレンの含有量は不飽和度として0.6~2.5モル%、分子量はムーニー粘度で25~55(125℃)であることが好ましい。
また、EPDMの存在比が20質量部未満では、必要とする接着力およびゴム付きが得られ難い。また80質量部を超えると、加硫速度が遅くなりホースの生産性が低下する。
アルキルフェノールホルムアルデヒド樹脂は、前記原料ゴムの加硫剤として作用することができる。
アルキルフェノールホルムアルデヒド樹脂には、ハロゲン化されたアルキルフェノールホルムアルデヒド樹脂(ハロゲン化アルキルフェノールホルムアルデヒド樹脂)も含まれる。中でも臭素化アルキルフェノールホルムアルデヒド樹脂が好ましい。
アルキルフェノールホルムアルデヒド樹脂としては、例えば田岡化学工業社製のタッキロール250-1等の市販品を使用することができる。
本発明で用いるカーボンブラックのコロイダル特性は、N2SA≧75m2/g、かつDBP吸油量≧90cm3/100gである。N2SAが75m2/g未満またはDBP吸油量が90cm3/100g未満であると、ガスバリア層の表面にゴム層を強固に接着することが困難になる。N2SAは80~150m2/gであることが好ましく、80~120m2/gであることがより好ましい。DBP吸油量は95~140cm3/100gであることが好ましく、100~130cm3/100gであることがより好ましい。
ここでN2SAとはカーボンブラックの表面に吸着する窒素分子量を意味し、具体的にはJIS K 6217-2に規定の方法で測定して求めた値を意味するものとする。
また、DBP吸油量はカーボンブラックの凝集体に吸収される油分量を意味し、具体的にはJIS K 6217-4に規定の方法で測定して求めた値を意味するものとする。
加硫助剤としては、例えば、アセチル酸、プロピオン酸、ブタン酸、ステアリン酸、アクリル酸、マレイン酸等の脂肪酸;アセチル酸亜鉛、プロピオン酸亜鉛、ブタン酸亜鉛、ステアリン酸亜鉛、アクリル酸亜鉛、マレイン酸亜鉛等の脂肪酸亜鉛が挙げられる。
加硫促進剤としては、例えば、テトラメチルチウラムジスルフィド(TMTD)、テトラエチルチウラムジスルフィド(TETD)等のチウラム系;ヘキサメチレンテトラミン等のアルデヒド・アンモニア系;ジフェニルグアニジン等のグアニジン系;ジベンゾチアジルジサルファイド(DM)等のチアゾール系;シクロヘキシルベンゾチアジルスルフェンアマイド等のスルフェンアミド系のものが挙げられる。
添加剤としては、例えば、クレー等の充填剤、パラフィン系オイル等の軟化剤、可塑剤、加工助剤、老化防止剤、顔料等が挙げられる。
内管層が上記に説明したような特定成分を特定含有量で含むガスバリア層およびゴム層からなるものでないと、接着剤を使用することなしにガスバリア層とゴム層とを強固に加硫接着することはできない。すなわち、高接着性(高接着力および高ゴム付き)を発現することはできない。
例えば内径は5~20mmであることが好ましく、7~17mmであることがより好ましい。
外管層の厚さは、1~5mmであるのが好ましく、0.5~3mmがより好ましく、1~2mmがさらに好ましい。
外管層が複数層で形成されていてもよい。
図1は本発明のホースの好適実施例を示す図である。
図1において本発明のホース1は、ガスバリア層21とその外表面に密着したゴム層22とからなる内管層を備えている。ガスバリア層21とゴム層22の間には、接着剤層は存在していないが、両層は強固に密着している。
また、本発明のホースは上記のように補強層を必ずしも有している必要はないが、補強層を備えていると、ホースの引張り破断強度、使用可能圧力範囲および金具装着性が向上するので好ましい。特に、本発明のホースを高圧部に用いる場合は、補強層を有することが好ましい。
本発明のホースの製造方法は特に限定されず、従来公知の方法を用いることができる。
例えばガスバリア層およびゴム層は押出し成形して得ることができる。ここで、ゴム層は上記の方法で得たゴム組成物を用いて成形することができる。例えば前述の図1を用いて説明した好適実施態様のホースの場合であれば、ガスバリア層の外表面にゴム層を積層し、さらに編組またはスパイラル巻などにより補強層、ついで外側ゴム層を積層した後、全体を加硫することによって得ることができる。加硫条件は約150~180℃で加硫を行なうことができる。
以下に示す原料を第1表~第3表に示す量比(質量部)で混合し、各実施例および各比較例におけるゴム組成物を得た。具体的には、BIMS、ブチルゴムおよび/またはハロゲン化ブチルゴム、ならびにEPDMに、カーボンブラック、パラフィン油、ステアリン酸を加え、ロール、バンバリーミキサー等により混合し、引き続いて、アルキルフェノールホルムアルデヒド樹脂、ZnOを加えて混合して組成物を得た。
塩素化ブチルゴム(Cl-IIR):EXXON CHLOROBUTYL 1066、日本ブチル株式会社製
臭素化ブチルゴム(Br-IIR):EXXON BROMOBUTYL 2255、日本ブチル株式会社製
BIMS:Exxpro 3745、EXXONMOBIL CHEMICAL COMPANY
EPDM:三井EPT4070、三井化学社製
カーボンブラック(C.B.(ISAF)):ショウブラックN220、昭和キャボット社製
カーボンブラック(C.B.(HAF)):ショウブラックN330、昭和キャボット社製
カーボンブラック(C.B.(FEF)):ショウブラックN550、昭和キャボット社製
ステアリン酸:ルナックYA、花王株式会社製
パラフィン油:プロセスオイル123、昭和シェル石油社製
ZnO:酸化亜鉛3種、正同化学工業社製
臭素化アルキルフェノールホルムアルデヒド樹脂:タッキロール250―1、田岡化学工業株式会社
また、小型スクリュー式押し出し機(スクリューは圧縮タイプを使用)に、丸棒状となるヘッドを組み付け、ヘッド、シリンダー温度を80℃、回転数を60rpmにて押し出し性を確認した。そして外観等、ホースとして使用可能なレベルにある形状のものを「○」、使用不可レベルにあるものを「×」として示した。
次に、得られた各ゴム組成物を150℃のプレス成型機を用い、面圧3.0MPaの圧力下で45分間加硫して、2mm厚の加硫シートを作製した。このシートからJIS3号ダンベル状の試験片を打ち抜き、引張速度500mm/分での引張試験をJIS K6251-2004に準拠して行い、引張強さ(TB)[MPa]、切断時伸び(EB)[%]、100%モジュラス(M100)〔MPa〕を室温にて測定した。
また、JIS K6253-2006のタイプAデュロメータに準じて、各ゴム組成物の硬化物の室温における硬さ(HS)を測定した。
各実施例および各比較例のゴム組成物および変性ポリアミドを用いて内管層からなるホースを作製した。
具体的には、初めに、ザイテルST811HS(表中では「ザイテル」と記す)またはポリアミド樹脂(表中では「PA6」と記す)を、押出し機を用いてマンドレル(外径11mm)の上に引き落として成型し、厚さ0.1mmのガスバリア層を形成した。
次に得られたゴム組成物を用いて、上記で得たガスバリア層の外表面に、厚さ1.4mmのゴム層を形成した。ガスバリア層の外側の表面にゴム層を積層した後、全体を加硫することによって得た。加硫条件は約150~180℃で蒸気圧をかけ加硫を行った。そして、1.5mmの厚さであって外径が14mmの内管層を得た。
なお、比較例1-1については、ガスバリア層とゴム層とを接着材(Chemlok 402X、Lord Corporation製)を用いて接着した。
ここで接着力は幅25mm当たりの接着力(N)を意味する。また、接着力が40N/25mm以上のものを「○」、接着力が40N/25mm未満のものを「×」として評価した。
また、ゴム付きはゴムが剥がれず残留している面積比(%)を意味する。また、これに加えて、剥がれずに残留したゴムの厚さも測定して「厚い」、「薄い」、「界面」(ガスバリア層とゴム層との界面で剥離したものを意味する。)で示した。そして、厚いものを「○(良好)」、「薄い」ものを「△」、「界面」で剥離したものを「×」と評価してこれを記した。
上記の試験3と同様の方法で、各実施例および各比較例におけるホースを作製した。ホースの内径は11mm、外径は18mm(内管層の厚さは1.5mmである)、長さは50cmとした。
次に、ホースに金具を装着後、冷媒(R-134a)を封入し、90℃のオーブンに24時間放置した。ここで冷媒は0.6g/cm3となるように封入した。
次に冷媒を解放後、ただちに120℃のオーブンに入れ、24時間放置した。
そして、その後、ホースを半分に切り(縦割り)、ゴム層の剥離(タナ落ち)を確認した。タナ落ちがなかったものを「○」、タナ落ちが発生したものを「×」として示す。
実施例3および実施例4におけるホースのそれぞれについて、ホース両端に金具を装着した長さ50cmのホース 4本を用意した。次にその中の3本について、0.6g/cm3となるように冷媒を封入した。また、残りの1本は冷媒を封入せずに密閉した。そして、100℃で24時間経過後における質量および96時間後における質量を測定することで、72時間当たりのガス透過量(g/m・72h)を算出し、R-134aの透過性を調べた。
比較例1-1はガスバリア層とゴム層とを接着剤で接着した態様である。この場合、ゴム付きが薄くなり、デラミネーション試験においてタナ落ちが生じ、ガスバリア層とゴム層との接着が不十分であることがわかった(第1表参照)。
なお、比較例1-2、比較例2、比較例3は特許文献3に記載の態様に相当する。また、比較例2は特許文献2に記載の態様にも相当する。
また、実施例3および実施例4におけるガス透過性試験の結果は、いずれも3.3[g/(m・72h)]となり、冷媒輸送用ホースとして好ましく適用できることが確認できた。
また、比較例10は、原料ゴム100質量部に対するカーボンブラックの添加量が85質量部であり、本発明の範囲外である。この場合、押し出し性が不十分であった。
なお、比較例13、14は特許文献1に記載の態様に相当する。
Claims (3)
- ガスバリア層とその外表面に密着したゴム層とからなる内管層を備える冷媒輸送用ホースであって、
前記ガスバリア層が、ポリアミドとカルボキシル基含有変性ポリオレフィンとをブレンドして得られる変性ポリアミドからなり、
前記ゴム層が、原料ゴム:100質量部に対して、アルキルフェノールホルムアルデヒド樹脂:1~15質量部、およびカーボンブラック:30~80質量部を配合してなるゴム組成物からなり、
前記原料ゴムが、BIMSと、ブチルゴムおよび/またはハロゲン化ブチルゴムである共重合ゴムと、EPDMとからなり、
前記原料ゴムにおける前記BIMSの含有量が5~40質量部であり、前記BIMSと前記共重合ゴムとの含有量の合計が20~80質量部であり、EPDMの含有量が80~20質量部であり、
前記カーボンブラックは、N2SA≧75m2/g、かつDBP吸油量≧90cm3/100gであり、
前記ガスバリア層と前記ゴム層との間に接着剤層を有さない、冷媒輸送用ホース。 - 前記共重合ゴムがハロゲン化ブチルゴムである、請求項1に記載の冷媒輸送用ホース。
- 前記ポリアミドが、ポリアミド6、ポリアミド11、ポリアミド12、ポリアミド4-6、ポリアミド6-6、ポリアミド6-10、ポリアミド6-12およびポリアミドMXD-6ならびにこれらの中の2種以上のコポリマーからなる群から選ばれる少なくとも1つである、請求項1または2に記載の冷媒輸送用ホース。
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JP7360034B2 (ja) * | 2019-11-28 | 2023-10-12 | 横浜ゴム株式会社 | 冷媒輸送用ホース |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2012091486A (ja) * | 2010-09-29 | 2012-05-17 | Tokai Rubber Ind Ltd | ホースの製法およびそれによって得られたホース |
JP2012177006A (ja) * | 2011-02-25 | 2012-09-13 | Tokai Rubber Ind Ltd | 冷媒輸送ホース用樹脂組成物およびその製法、並びに冷媒輸送ホース |
JP2017025169A (ja) * | 2015-07-17 | 2017-02-02 | 横浜ゴム株式会社 | 熱可塑性樹脂フィルムとゴムの積層体、インナーライナー材および空気入りタイヤ |
US11077710B2 (en) | 2015-07-17 | 2021-08-03 | The Yokohama Rubber Co., Ltd. | Laminate of thermoplastic resin film and rubber, inner liner material, and pneumatic tire |
JP2018135424A (ja) * | 2017-02-21 | 2018-08-30 | 株式会社ブリヂストン | 冷媒輸送ホース用ポリアミド樹脂組成物及びこれを用いた冷媒輸送ホース |
JP2019072854A (ja) * | 2017-10-12 | 2019-05-16 | 横浜ゴム株式会社 | ポリイミドフィルムとゴム組成物の層の積層体およびそれを含む空気入りタイヤ |
JPWO2023007940A1 (ja) * | 2021-07-29 | 2023-02-02 | ||
WO2023007940A1 (ja) * | 2021-07-29 | 2023-02-02 | 横浜ゴム株式会社 | 冷媒搬送用ホース |
JP7453603B2 (ja) | 2021-07-29 | 2024-03-21 | 横浜ゴム株式会社 | 冷媒搬送用ホース |
Also Published As
Publication number | Publication date |
---|---|
TWI372221B (en) | 2012-09-11 |
KR101059714B1 (ko) | 2011-08-29 |
KR20100095497A (ko) | 2010-08-31 |
EP2311633A4 (en) | 2011-08-03 |
IN2009KN03848A (ja) | 2015-08-28 |
CN101855075A (zh) | 2010-10-06 |
TW201024581A (en) | 2010-07-01 |
EP2311633A1 (en) | 2011-04-20 |
JPWO2010073375A1 (ja) | 2012-05-31 |
JP4365454B1 (ja) | 2009-11-18 |
EP2311633B1 (en) | 2012-08-15 |
CN101855075B (zh) | 2013-04-17 |
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