WO2012096031A1 - Composition de caoutchouc et pièce de système d'alimentation en carburant pour automobiles l'utilisant - Google Patents
Composition de caoutchouc et pièce de système d'alimentation en carburant pour automobiles l'utilisant Download PDFInfo
- Publication number
- WO2012096031A1 WO2012096031A1 PCT/JP2011/070463 JP2011070463W WO2012096031A1 WO 2012096031 A1 WO2012096031 A1 WO 2012096031A1 JP 2011070463 W JP2011070463 W JP 2011070463W WO 2012096031 A1 WO2012096031 A1 WO 2012096031A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- weight
- parts
- rubber composition
- nbr
- Prior art date
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 51
- 229920001971 elastomer Polymers 0.000 title claims abstract description 41
- 239000005060 rubber Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000004073 vulcanization Methods 0.000 claims abstract description 34
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 31
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 26
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 21
- -1 2-ethylhexyl Chemical group 0.000 claims abstract description 8
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 abstract description 18
- 230000006835 compression Effects 0.000 abstract description 17
- 238000007906 compression Methods 0.000 abstract description 17
- 238000003860 storage Methods 0.000 abstract description 17
- 238000005336 cracking Methods 0.000 abstract description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 229960002447 thiram Drugs 0.000 description 17
- 239000003502 gasoline Substances 0.000 description 12
- 239000004014 plasticizer Substances 0.000 description 10
- 230000003712 anti-aging effect Effects 0.000 description 9
- 235000014692 zinc oxide Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 239000006237 Intermediate SAF Chemical class 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/40—Thiurams, i.e. compounds containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
-
- 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
- F16L11/06—Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
- F02M37/0011—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor
- F02M37/0017—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor related to fuel pipes or their connections, e.g. joints or sealings
Definitions
- the present invention relates to a rubber composition used for an automobile fuel member and an automobile fuel member using the same, and more specifically, a filler neck tube, a breather hose, and an evaporator that are in contact with fuel (gasoline, gasoline vapor, etc.).
- a rubber composition used for automobile fuel seals such as fuel tanks, gaskets, O-rings, etc. that contact with fuel (gasoline, gasoline vapor, etc.)
- the present invention relates to an automobile fuel member.
- a rubber composition used for an automobile fuel member such as an automobile fuel transportation hose
- a blend rubber (NBR-PVC) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC), or NBR is used.
- NBR-PVC blend rubber
- PVC polyvinyl chloride
- a low molecular weight thiuram vulcanization accelerator such as tetramethylthiuram disulfide (TMTD) or a sulfenamide vulcanization accelerator is used (see Patent Documents 1 to 4). ).
- JP 2001-72804 A JP 2001-317663 A JP 2008-208267 A JP 2009-1657 A
- low molecular weight thiuram vulcanization accelerators and sulfenamide vulcanization accelerators such as the above-mentioned TMTD have high reaction activity, poor storage stability when rubber is not vulcanized, and dense vulcanization density. Therefore, when it is immersed in fuel oil, it is easy to produce a crack, and there exists a difficulty that it is inferior to solvent crack resistance (performance which suppresses generation
- the content of the low molecular weight thiuram vulcanization accelerator or sulfenamide vulcanization accelerator such as TMTD is reduced, the storage stability and the solvent crack resistance are improved, but the compression set is improved. A new problem of inferiority will occur.
- the present invention has been made in view of such circumstances, and provides a rubber composition excellent in all of the performances of storage stability, solvent crack resistance, and compression set, and an automobile fuel member using the rubber composition. Is the purpose.
- the present invention is a rubber composition used for a fuel member for automobiles, comprising the following (A) as a main component and containing only the following component (B) as a vulcanization accelerator. And let the rubber composition whose content of the said (B) component exceeds 2.5 weight part with respect to 100 weight part of said (A) components be a 1st summary.
- A Blend rubber (NBR-PVC) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC), or NBR.
- NBR-PVC Blend rubber
- NBR acrylonitrile-butadiene rubber
- PVC polyvinyl chloride
- TTZT tetrabenzyl thiuram disulfide
- TOT-N tetrabis (2-ethylhexyl) thiuram disulfide
- the second gist of the present invention is an automobile fuel member using the rubber composition as at least a part of an automobile fuel member.
- TMTD tetramethylthiuram disulfide
- TZT tetrabenzylthiuram disulfide
- TOT-N tetrabis (2-ethylhexyl) thiuram disulfide
- the rubber composition used in the automobile fuel member of the present invention (hereinafter sometimes simply referred to as “rubber composition”) has tetrabenzylthiuram disulfide (TBZT) and tetrabis (TBZT) as vulcanization accelerators.
- TTZT-N 2-ethylhexyl) thiuram disulfide
- component B both of the above TBZT and TOT-N [hereinafter sometimes simply referred to as “TBZT and TOT-N (component B)]” Since the content is set to exceed 2.5 parts by weight with respect to 100 parts by weight of NBR-PVC or NBR (component A), all of storage stability, solvent crack resistance and compression set The effect of excellent performance is obtained.
- the rubber composition of the present invention further contains stearic acid and zinc oxide in addition to the A component and the B component, and the stearic acid content is 0.5 to 100 parts by weight based on 100 parts by weight of the A component.
- the content of zinc oxide is 3 to 10 parts by weight with respect to 100 parts by weight of the component A, stearic acid is used rather than the reaction between the decomposition product of the component B and zinc oxide. Since the reaction between zinc and zinc oxide is prioritized, the balance between storage stability, solvent crack resistance and compression set becomes better.
- An automotive fuel member (automotive fuel transportation hose or automotive fuel seal) using at least a part (or all of the rubber composition) of the present invention is immersed in fuel oil. Since crack generation can be suppressed, it has excellent solvent crack resistance.
- the rubber composition used for the fuel member for automobiles of the present invention includes a blend rubber (NBR-PVC) or NBR (component A) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC), tetrabenzyl thiuram disulfide ( TBZT) and tetrabis (2-ethylhexyl) thiuram disulfide (TOT-N) (B component).
- NBR-PVC blend rubber
- NBR acrylonitrile-butadiene rubber
- PVC polyvinyl chloride
- TBZT tetrabenzyl thiuram disulfide
- TOT-N tetrabis (2-ethylhexyl) thiuram disulfide
- the range is / 20 to 70/30.
- the NBR is preferably one having an acrylonitrile (AN) amount in the range of 25 to 65%, particularly preferably an AN amount in the range of 30 to 60%, from the viewpoint of the balance between the fuel barrier resistance and the low temperature property.
- AN acrylonitrile
- a monomer copolymerizable with the NBR may be blended.
- the PVC preferably has an average degree of polymerization in the range of 700 to 1400, particularly preferably around 800.
- NBR-PVC in which PVC is blended with NBR is more preferable than NBR alone from the viewpoint of ozone resistance.
- component A is the main component
- the phrase “component A is the main component” means that the component A is the main component in the rubber composition of the present invention.
- both TBZT and TOT-N (component B) >>
- thiuram vulcanization accelerators such as tetramethylthiuram disulfide (TMTD) and sulfenamide vulcanization accelerators are used. Contains no agent.
- the total content of both TBZT and TOT-N exceeds 2.5 parts by weight with respect to 100 parts by weight of NBR-PVC or NBR (component A), preferably It is 5 parts by weight or more, most preferably in the range of 5 to 7 parts by weight. That is, if the content of the component B is too small, the compression set is inferior.
- the rubber composition of the present invention includes a processing aid, an antioxidant, a reinforcing agent, a plasticizer, Vulcanizing agents, vulcanization accelerating aids, vulcanization retarders, white fillers, colorants and the like may be appropriately blended as necessary.
- processing aids include stearic acid, fatty acid esters, fatty acid amides, hydrocarbon resins and the like, and are used alone or in combination of two or more.
- stearic acid is preferable from the viewpoint of the balance between storage stability, solvent crack resistance, and compression set.
- the content of the processing aid is usually set in the range of 0.1 to 10 parts by weight, preferably 0.5 to 1.5 parts per 100 parts by weight of the NBR-PVC or NBR (component A).
- the range is parts by weight.
- Anti-aging agent examples include phenylenediamine-based anti-aging agents, phenol-based anti-aging agents, diphenylamine-based anti-aging agents, quinoline-based anti-aging agents, waxes and the like, and are used alone or in combination of two or more. .
- the content of the anti-aging agent is usually set in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the component A.
- ⁇ Reinforcing agent examples include carbon black, silica and the like, and they are used alone or in combination of two or more.
- Examples of the carbon black include grades such as SAF class, ISAF class, HAF class, MAF class, FEF class, GPF class, SRF class, FT class, and MT class. These may be used alone or in combination of two or more.
- the content of the reinforcing agent is usually set in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the component A.
- plasticizer examples include phthalic acid plasticizers such as di-2-ethylhexyl phthalate (DOP) and di-n-butyl phthalate (DBP), and adipic acid such as dibutyl carbitol adipate and dioctyl adipate (DOA).
- Plasticizers, sebacic acid plasticizers such as dioctyl sebacate (DOS), dibutyl sebacate (DBS), phosphate plasticizers such as tricresyl phosphate (TCP), and polyether plasticizers. . These may be used alone or in combination of two or more.
- the content of the plasticizer is usually set in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the component A.
- vulcanizing agent examples include sulfur compounds such as sulfur, morpholine and disulfide, organic peroxides, and the like, and they are used alone or in combination of two or more.
- the content of the vulcanizing agent is usually set in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the component A.
- vulcanization acceleration aid examples include zinc oxide, activated zinc white, magnesium oxide, and the like, and they are used alone or in combination of two or more. Among these, zinc oxide is preferable from the viewpoint of balance between storage stability, solvent crack resistance, and compression set.
- the content of the vulcanization accelerator aid is usually set in the range of 0.5 to 10 parts by weight, preferably in the range of 3 to 10 parts by weight, with respect to 100 parts by weight of the component A.
- vulcanization retarder examples include N- (cyclohexylthio) phthalimide.
- the content of the vulcanization retarder is usually set in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the component A.
- filler examples include calcium carbonate, magnesium carbonate, clay, talc, mica and the like, and they are used alone or in combination of two or more.
- the content of the filler is usually set in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the component A.
- the rubber composition of the present invention contains a predetermined amount of both TBZT and TOT-N (component B) in the NBR-PVC or NBR (component A), and, if necessary, carbon black, an antioxidant, etc. And kneading them using a kneader such as a kneader, a Banbury mixer, or a roll.
- a kneader such as a kneader, a Banbury mixer, or a roll.
- the rubber composition of the present invention is used for at least a part (or all) of an automobile fuel member such as an automobile fuel transport hose or an automobile fuel seal.
- an automobile fuel member such as an automobile fuel transport hose or an automobile fuel seal.
- the fuel transportation hose for automobiles include a filler neck tube, a breather hose, an evaporation hose, a purge hose, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
- Examples of the automobile fuel seal include tank packing, gaskets, O-rings, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
- the automobile fuel transport hose of the present invention (hereinafter, abbreviated as “fuel transport hose” as appropriate) can be produced, for example, as follows. That is, the rubber composition prepared as described above is extruded using an extruder, and this is steam vulcanized (for example, 155 ° C. ⁇ 20 minutes) to obtain a fuel transport hose having a single layer structure. be able to. Note that a mandrel may be used as necessary.
- a glycol-based mold release agent for example, polyethylene glycol (PEG), polypropylene glycol (PPG) and a mixture thereof
- silicone emulsion-based mold release is provided on either or both of the inner peripheral surface of the hose and the outer peripheral surface of the mandrel.
- a release agent such as an agent may be applied.
- the fuel transport hose of the present invention is not limited to a single layer structure, and may have a multilayer structure in which at least one layer is formed on the outer periphery thereof, and may be reinforced to a part of the multilayer structure hose.
- a layer may be formed.
- the inner diameter of the hose is preferably in the range of 2 to 100 mm, particularly preferably in the range of 5 to 50 mm, and the thickness of the hose is preferably in the range of 0.5 to 20 mm, particularly preferably 1 to 10 mm. Range.
- Nipol DN508SCR (AN amount: 38.0%) manufactured by Nippon Zeon
- TZT Tetrabenzylthiuram disulfide
- component B Accelerator TBZT, manufactured by Kawaguchi Chemical Co., Ltd.
- TOT-N Tetrabis (2-ethylhexyl) thiuram disulfide (component B)] Nouchira TOT-N, manufactured by Ouchi Shinsei Chemical Co., Ltd.
- TMTD Tetramethylthiuram disulfide
- Stearic acid manufactured by Kao Corporation, LUNAC S-70V
- Anti-aging agent (i) ANTAGE 3C, manufactured by Kawaguchi Chemical Co., Ltd.
- Anti-aging agent (ii)) ANTAGE RD manufactured by Kawaguchi Chemical Co., Ltd.
- Examples 1 to 6, Comparative Examples 1 to 3 The components shown in Table 1 below were blended in the proportions shown in the same table, and kneaded using a 3 L kneader to prepare a rubber composition. Next, the rubber composition was extruded with an extruder and steam vulcanized (155 ° C. ⁇ 20 minutes) to produce a fuel transport hose having a single layer structure (inner diameter 30 mm, thickness 3 mm).
- Examples 1 to 6 contain only a predetermined amount of TBZT and TOT-N as specific vulcanization accelerators (component B), so that storage stability, solvent crack resistance, compression It was excellent in all the properties of permanent distortion.
- Comparative Examples 1 to 3 were inferior in any of storage stability, solvent crack resistance, and compression set properties.
- the rubber composition of the present invention is used in automobile fuel members such as automobile fuel transport hoses and automobile fuel seals.
- automobile fuel members such as automobile fuel transport hoses and automobile fuel seals.
- the fuel transportation hose for automobiles include a filler neck tube, a breather hose, an evaporation hose, a purge hose, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
- automobile fuel seal include tank packing, gaskets, O-rings, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1304367.4A GB2501173B (en) | 2011-01-14 | 2011-09-08 | Rubber composition and automobile fuel system part using same |
JP2012552625A JP5655096B2 (ja) | 2011-01-14 | 2011-09-08 | ゴム組成物およびそれを用いた自動車用燃料部材 |
CN201180059193.2A CN103249772B (zh) | 2011-01-14 | 2011-09-08 | 橡胶组合物和使用其的汽车用燃料构件 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-006045 | 2011-01-14 | ||
JP2011006045 | 2011-01-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012096031A1 true WO2012096031A1 (fr) | 2012-07-19 |
Family
ID=46506948
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/070463 WO2012096031A1 (fr) | 2011-01-14 | 2011-09-08 | Composition de caoutchouc et pièce de système d'alimentation en carburant pour automobiles l'utilisant |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP5655096B2 (fr) |
CN (1) | CN103249772B (fr) |
GB (1) | GB2501173B (fr) |
WO (1) | WO2012096031A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015123676A (ja) * | 2013-12-26 | 2015-07-06 | ダイキン工業株式会社 | 積層体 |
JP2018052054A (ja) * | 2016-09-30 | 2018-04-05 | 住友理工株式会社 | ホースの製造方法 |
JP2019199549A (ja) * | 2018-05-16 | 2019-11-21 | Nok株式会社 | ゴム組成物およびシール材 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105273329A (zh) * | 2014-06-25 | 2016-01-27 | 苏州辛帝斯燃气密封材料有限公司 | 一种家用燃气软管及其加工工艺及专用生产设备 |
CN104592589B (zh) * | 2015-01-01 | 2016-10-05 | 宁波帝杨电子科技有限公司 | 一种丁腈橡胶/聚氯乙烯复合材料及其制备方法 |
CN107474436A (zh) * | 2017-08-31 | 2017-12-15 | 徐州市恒基伟业建材发展有限公司 | 一种用于制作汽车油箱的塑料配方 |
CN113896963A (zh) * | 2021-11-25 | 2022-01-07 | 南阳天一密封股份有限公司 | 一种承耐混合燃料系统橡胶密封材料及其制备工艺 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001072804A (ja) * | 1999-06-28 | 2001-03-21 | Tokai Rubber Ind Ltd | ゴム組成物及び自動車用燃料輸送ホース |
JP2001317663A (ja) * | 2000-05-11 | 2001-11-16 | Tokai Rubber Ind Ltd | 燃料輸送ホース |
WO2007145026A1 (fr) * | 2006-06-16 | 2007-12-21 | Nok Corporation | Stratifié métal-caoutchouc |
JP2008239832A (ja) * | 2007-03-28 | 2008-10-09 | Jsr Corp | ゴム組成物、架橋ゴム、及び成形品 |
JP2009001657A (ja) * | 2007-06-21 | 2009-01-08 | Yokohama Rubber Co Ltd:The | ホース用接着性ゴム組成物 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5096764B2 (ja) * | 2007-02-27 | 2012-12-12 | 東海ゴム工業株式会社 | 自動車用非水系ホース |
JP2010155883A (ja) * | 2008-12-26 | 2010-07-15 | Nippon Zeon Co Ltd | ニトリル共重合体ゴム組成物 |
-
2011
- 2011-09-08 WO PCT/JP2011/070463 patent/WO2012096031A1/fr active Application Filing
- 2011-09-08 GB GB1304367.4A patent/GB2501173B/en active Active
- 2011-09-08 JP JP2012552625A patent/JP5655096B2/ja active Active
- 2011-09-08 CN CN201180059193.2A patent/CN103249772B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001072804A (ja) * | 1999-06-28 | 2001-03-21 | Tokai Rubber Ind Ltd | ゴム組成物及び自動車用燃料輸送ホース |
JP2001317663A (ja) * | 2000-05-11 | 2001-11-16 | Tokai Rubber Ind Ltd | 燃料輸送ホース |
WO2007145026A1 (fr) * | 2006-06-16 | 2007-12-21 | Nok Corporation | Stratifié métal-caoutchouc |
JP2008239832A (ja) * | 2007-03-28 | 2008-10-09 | Jsr Corp | ゴム組成物、架橋ゴム、及び成形品 |
JP2009001657A (ja) * | 2007-06-21 | 2009-01-08 | Yokohama Rubber Co Ltd:The | ホース用接着性ゴム組成物 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015123676A (ja) * | 2013-12-26 | 2015-07-06 | ダイキン工業株式会社 | 積層体 |
JP2018052054A (ja) * | 2016-09-30 | 2018-04-05 | 住友理工株式会社 | ホースの製造方法 |
JP2019199549A (ja) * | 2018-05-16 | 2019-11-21 | Nok株式会社 | ゴム組成物およびシール材 |
Also Published As
Publication number | Publication date |
---|---|
GB201304367D0 (en) | 2013-04-24 |
CN103249772B (zh) | 2014-12-17 |
GB2501173A8 (en) | 2015-11-11 |
GB2501173B (en) | 2017-06-14 |
GB2501173A (en) | 2013-10-16 |
CN103249772A (zh) | 2013-08-14 |
JPWO2012096031A1 (ja) | 2014-06-09 |
JP5655096B2 (ja) | 2015-01-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5655096B2 (ja) | ゴム組成物およびそれを用いた自動車用燃料部材 | |
JP6186251B2 (ja) | インナーライナー用ゴム組成物及び空気入りタイヤ | |
EP3184325B1 (fr) | Bandage pneumatique pour une charge lourde | |
WO2013105655A1 (fr) | Composition de caoutchouc pour bandes transporteuses, caoutchouc pour revêtements de bande transporteuse et bande transporteuse | |
JPWO2019124462A1 (ja) | ゴム組成物及びゴム成形品 | |
WO2012096030A1 (fr) | Composition de caoutchouc et pièce de système d'alimentation en carburant pour automobiles l'utilisant | |
WO2015186482A1 (fr) | Composition de caoutchouc amortisseur de vibrations et amortisseur de vibrations en caoutchouc | |
JP6512576B2 (ja) | ホース | |
WO2014109219A1 (fr) | Composition de caoutchouc pour caoutchouc anti-vibration | |
JP5991855B2 (ja) | ゴム組成物 | |
JP2016098296A (ja) | インナーライナー用未加硫ゴム組成物および空気入りタイヤ | |
JP2001317663A (ja) | 燃料輸送ホース | |
JP2013227480A (ja) | ゴム組成物 | |
JP4954611B2 (ja) | エピクロルヒドリンゴム組成物およびそれからなる成形体 | |
JP6099429B2 (ja) | タイヤ用サイドゴム組成物及びタイヤ | |
WO2014203695A1 (fr) | Composition de caoutchouc pour caoutchouc résistant aux vibrations | |
JP2009030037A (ja) | 防振ゴム組成物および防振部材 | |
JP6242832B2 (ja) | サイドウォール用ゴム組成物及びこれを使用する空気入りタイヤ | |
JP7382213B2 (ja) | 燃料ホース用ゴム組成物およびそれを用いて得られる燃料ホース | |
JP2009091375A (ja) | ゴム組成物 | |
JP5998490B2 (ja) | 空気ばね用ゴム組成物 | |
WO2024162168A1 (fr) | Tuyau de fluide | |
JP2016196562A (ja) | ゴム組成物およびそれを用いた空気入りタイヤ | |
JP2006249367A (ja) | ヒドリンゴム組成物 | |
JP2009132835A (ja) | タイヤインナーライナー用ゴム組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11855478 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 1304367 Country of ref document: GB Kind code of ref document: A Free format text: PCT FILING DATE = 20110908 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1304367.4 Country of ref document: GB |
|
ENP | Entry into the national phase |
Ref document number: 2012552625 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11855478 Country of ref document: EP Kind code of ref document: A1 |