GB2501173A - Rubber composition and automobile fuel system part using same - Google Patents
Rubber composition and automobile fuel system part using same Download PDFInfo
- Publication number
- GB2501173A GB2501173A GB1304367.4A GB201304367A GB2501173A GB 2501173 A GB2501173 A GB 2501173A GB 201304367 A GB201304367 A GB 201304367A GB 2501173 A GB2501173 A GB 2501173A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- parts
- component
- automobile fuel
- rubber composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 229920001971 elastomer Polymers 0.000 title claims abstract description 43
- 239000005060 rubber Substances 0.000 title claims abstract description 43
- 238000004073 vulcanization Methods 0.000 claims abstract description 35
- 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 30
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 26
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 25
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 22
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- 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
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 230000006835 compression Effects 0.000 abstract description 19
- 238000007906 compression Methods 0.000 abstract description 19
- 238000005336 cracking Methods 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 18
- -1 2-ethylhexyl Chemical group 0.000 abstract description 2
- 230000035882 stress Effects 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 14
- 230000003078 antioxidant effect Effects 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 13
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229960002447 thiram Drugs 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 235000019241 carbon black Nutrition 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 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
- 239000012744 reinforcing agent Substances 0.000 description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 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 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 238000012856 packing Methods 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
- 229920006602 NBR/PVC Polymers 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
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 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
- 238000004898 kneading Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000002093 peripheral effect Effects 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
- 230000009257 reactivity Effects 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 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
- 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
- 239000005062 Polybutadiene Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910000019 calcium carbonate 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
- 230000002542 deteriorative effect Effects 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- WSUTUEIGSOWBJO-UHFFFAOYSA-N dizinc oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Zn+2] WSUTUEIGSOWBJO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 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
- 239000007788 liquid Substances 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
- 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
- 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
- 239000003921 oil Substances 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide 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
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 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
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
The purpose of the invention is to provide a rubber composition that performs well in terms of storage stability, solvent stress cracking resistance, and permanent compression strain, and is used as an automobile fuel system part. The rubber composition that is used for automobile fuel system parts comprises (A) as the main component, contains Component (B) alone as the vulcanization accelerator, and the content of Component (B) exceeds 2.5 parts by weight with respect to 100 parts by weight of Component (A). (A) A blended rubber (NBR-PVC) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC), or NBR (B) Both tetrabenzyl thiuram disulfide (TBZT) and tetrabis (2-ethylhexyl) thiuram disulfide (TOT-N)
Description
RUBBER COMPOSITION AND AUTOMOBILE FUEL SYSTEM PART USING SAME
Technical Field
The present invention relates to a rubber composition for use in an automobile fuel system part and an automobile fuel system part using the same and, more specifically, to: a rubber composition for use in an automobile fuel delivery hose which is brought into contact with a fuel (such as gasoline or gasoline steam); a rubber composition for use in an automobile fuel seal which is brought into contact with a fuel (such as gasoline or gasoline steam), such as a tank packing, a gasket, or an 0-ring; and an automobile fuel system part using the rubber composition.
Background Art
Hitherto, compositions containing, a blended rubber (NJBR-PVC) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC) or NBR as a main component and further containing a low-molecular-weight thiuram-based vulcanization accelerator or sulfenamide-based vulcanization accelerator such as tetramethyithiuram disulfide (TMTD) have been used as rubber compositions to be used for an automobile fuel system part such as an automobile fuel delivery hose (see Patent Literatures 1 to 4).
Citation List Patent Literature 1)JP2001-72804A 2) JP 2001-317663 A 3) JP 2008-208267 A 4) JP 2009-1657 A
Summary of Invention
Technical Problem However, the low-molecular-weight thiuram-based vulcanization accelerator or sulfenamide-based vulcanization accelerator such as TMTD has high reactivity, has poor storage stability when the rubber is unvulcanized, and causes an increase in vulcanization density.
Therefore, the rubber composition tends to cause cracks when immersed in a fuel oil and is poor in solvent stress cracking resistance (performance in suppressing the occurrence of solvent * cracks). On the other hand, when the content of the low-molecular-weight thiuram-based vulcanization accelerator or sulfenamide-based vulcanization accelerator such as TMTD is reduced, the storage stability and solvent stress cracking resistance are improved, but there arises another problem in that the permanent compression set property is poor.
The present invention has been made in view of the circumstances as described above, and an object of the present invention is to provide a rubber composition that has excellent storage stability, solvent stress cracking resistance, and permanent compression set property, and an automobile fuel system part using the same.
Solution to Problem In order to achieve the above-mentioned object, a first aspect of the present invention is a rubber composition to be used for an automobile fuel system part, including: the following component (A) as a main component; and the following components (B) alone as vulcanization accelerators, in which the content of the components (B) exceeds 2.5 parts by weight with respect to 100 parts by weight of the component (A).
(A) A blended rubber (NBR-PVC) of acryloriitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC), or NBR.
(B) Both tetrabenzylthiuram disulfide (TBZT) and tetrabis(2-ethylhexyi)thiuram disulfide (TOT-N).
In addition, a second aspect of the present invention is an automobile fuel system part, including the above-mentioned rubber composition in at least one part of the automobile fuel system part.
The inventor of the present invention has made extensive studies on a vulcanization accelerator alternative to the ow-molecular-weight thiuram-based vulcanization accelerator or sulfenamide-based vulcanization accelerator such as tetramethyithiuram disulfide (TMTD). In the course of the studies, the inventor of the present invention has focused attention on * tetrabenzylthiuram disulfide (TBZT) and tetrabis(2-ethylhexyl)thiuram disulfide (TOT-N), which have high molecular weights, among the thiuram-based vulcanization accelerators. The inventor has found that when TBZT and TOT-N only are used as the vulcanization accelerators, the occurrence of cracks when immersed in a fuel oil can be suppressed to improve the solvent stress cracking resistance because the components can reduce the reactivity to lower the vulcanization start speed, improve the storage stability when the rubber is unvulcanized, and suppress the increase in the vulcanization density. Further, the inventor has found that, when the content of the TBZT and TOT-N is set so as to exceed 2.5 parts by weight with respect to 100 parts by weight of NBR-PVC or NBR, the permanent compression set property is improved without deteriorating both the storage stability and solvent stress cracking resistance, thereby obtaining a rubber composition having excellent storage stability, solvent stress cracking resistance, and permanent compression set property, thus achieving the present invention.
Advantageous Effects of Invention As mentioned above, the rubber composition for use in an automobile fuel system part (hereinafter, sometimes simply referred to as "rubber composition") of the present invention is excellent in each and every performance of storage stability, solvent-stress-cracking resistance, and permanent compression set property because the composition contains tetrabenzylthiuram disulfide (TBZT) and tetrabis(2-ethylhexyl)thiuram disulfide (TOT-N) only as vulcanization accelerators! in which the content of both the TBZT and TOT-N (components (B)) (hereinafter, sometimes simply abbreviated as "TBZT and TOT-N (components (B))" is set so as to exceed 2.5 parts by weight with respect to 100 parts by weight of NBR-PVC or NBR (component (A)).
In addition, when the mixing ratio by weight of TBZT (81) to TOT-N (82) of the components (B) falls within the range of B1/B2=99/1 to 50/50, the composition is excellent in a balance among each and every performance of storage stability, solvent stress cracking * resistance, and permanent compression set property.
When the rubber composition of the present invention further contains stearic acid and zinc oxide in addition to the component (A) and components (B), in which the content of the stearic acid is 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the component (A), and the content of the zinc oxide is 3 to 10 parts by weight with respect to 100 parts by weight of the component (A), the composition is better in the balance among storage stability, solvent stress cracking resistance, and permanent compression set property because a reaction of stearic acid with zinc oxide preferentially occurs compared with a reaction of degraded products of the components (B) with zinc oxide.
Further, the automobile fuel system part (automobile fuel delivery hose or automobile fuel seal) that includes, the rubber composition of the present invention in at least one part (or for the whole) can suppress the occurrence of cracks when immersed in a fuel oil and hence is excellent in solvent stress cracking resistance.
Description of Embodiments
Next, embodiments of the present invention are described in detail. However, the present invention is not limited to the embodiments.
A rubber composition for use in an automobile fuel system part of the present invention a can be obtained by using: a blended rubber (NBR-PVC) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC) or NOR (component (A)); and both tetrabenzylthiuram disulfide (TBZT) and tetrabis(2-ethylhexyl)thiuram disulfide (TOT-N) (components (B)). In the present invention, the composition contains the TBZT and TOT-N alone as vulcanization accelerators, in which the content of both the TBZT and TOT-N (components (B)) is set so as to exceed 2.5 parts by weight with respect to 100 parts by weight of NOR-PVC or NBR (component (A)). This is the greatest characteristic of the present invention.
* Next, the components are described.
NBR-PVC or NBR (component (A)) The blending ratio (weight ratio) of NBR to PVC in the NOR-PVC falls preferably within the range of NBR/PVC=85/1 5 to 65/35, particularly preferably NBR/PVC=80120 to 70(30 from the viewpoint of ozone resistance.
The NBR contains acrylonitrile (AN) in an amount of preferably from 25 to 65%, particularly preferably from 30 to 60% from the viewpoint of a balance between fuel barrier property and low-temperature property.
It should be noted that a monomer copolymerizable with the NBR may be blended in the present invention.
In addition, the PVC preferably has an average polymerization degree of 700 to 1400, particularly preferably about 800.
From the viewpoint of ozone resistance, the component (A) in the rubber composition of the present invention is preferably NBR-PVC obtained by blending PVC in NBR compared with NBR alone.
It should be noted that, in the present invention, the phrase "including component (A) as a main component" means that component (A) is a major component in the rubber composition of the present invention.
Both TBZT and TOT-N (components (B)): In the rubber composition of the present invention TBfl and TOT-N only are used as vulcanization accelerators, and the composition does not contain a thiuram-based vulcanization accelerator such as tetramethylthiuran, disulfide (TMTD) or a sulfenamide-based vulcanization accelerator.
In the present invention, the total content of both the TBZT and TOT-N (components (B)) exceeds 2.5 parts by weight, and is preferably 5 parts by weight or more, most preferably from 5 to 7 parts by weight with respect to 100 parts by weight of the NBR-PVC or NBR (component (A)).
That is, when the content of the components (B) is too small, the composition is inferior in permanent compression set property.
The mixing ratio by weight of TBZT (81) to TOT-N (B2) in the components (B) preferably falls within the range of Bi/B2=99/1 to 50/50, particularly preferably B1/B2=90/1O to 55/45, most preferably B1/B2=80/20 to 60(40. When the mixing ratio of TBZT (Bi) is too large (the mixing ratio of TOT-N (B2) is too small), the permanent compression set property tends to deteriorate because of insufficient crosslinking. On the other hand, when the mixing ratio of TBZT (81) is too small (the mixing ratio of TOT-N (52) is too large1 the solvent stress cracking resistance tends to deteriorate, It should be noted that a processing aid, an antioxidant, a reinforcing agent, a plasticizer, a vulcanizing agent, a vulcanization accelerating aid, a vulcanization retarder, a white filler, or a colorant may be appropriately blended in the rubber composition of the present invention in addition to the NBR-PVC or NBR (component (A)) and specific vulcanization accelerators (components (B)).
Processing aid: Examples of the processing aid include stearic acid, a fatty acid ester, a fatty acid amide, and a hydrocarbon resin. One kind of processing aid is used alone, or two or more kinds thereof are used in combination, Of those, stearic acid is preferred from the viewpoint of a balance among storage stability, solvent stress cracking resistance, and permanent compression set property, The content of the processing aid is set within the range of typically 0.1 to 10 parts by weight, preferably 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the NBR-PVC or NBR (component (A)).
Antioxidant: Examples of the antioxidant include a phenylenediaminebased antioxidant, a phenol-based antioxidant, a diphenylamine_based antioxidant, a quinoline-base antioxidant, and waxes. One kind of those antioxidants is used alone or two or more kinds thereof are used in combination The content of the antioxidant is set within the range of typically 0ito 10 parts by weight with respect to 100 parts by weight of the component (A).
Reinforcing agent: Examples of the reinforcing agent include carbon black and silica. One kind of reinforcing agent is used alone! or two or more kinds thereof are used in combination.
Examples of the carbon black include SAF-grade, ISAF-grade HAF-grade MAF-grade, FEF-grade, GFF-grade, SRF-grade FT-grade, and MT-grade carbon blacks. One kind of those carbon blacks is used alone, or two or more kinds thereof are used in combination.
The content of the reinforcing agent is set within the range of typically 10 to 200 parts by weight with respect to 100 parts by weight of the component (A).
Plasticizer: Examples of the plasticizer include: a phthalate-based plasticizer such as di-2-ethylhexyl phthalate (DOP) or di-n-butyl phthalate (DOP); an adipate-based plasticizer such as dibutyl carbitol adipate or dioctyl adipate (DOA); a sebacate-based plasticizer such as dioctyl sebacate
S
(DOS) or dibutyl sebacate (DBS); a phosphate-based plasticizer such as tricresyl phosphate (TCP); and a polyether-based plasticizer. One kind of those plasticizers is used alone, or two or more kinds thereof are used in combination.
The content of the plasticizer is set within the range of typically 5 to 100 parts by weight with respect to 100 parts by weight of the component (A).
Vulcanizing agent: Examples of the vulcanizing agent include sulfur, morpholine, a sulfur compound such as a disulfide, and an organic peroxide. One kind of those agents is used alone, or two or more kinds thereof are used in combination.
The content of the vulcanizing agent is set within the range of typically 0.2 to 5 parts by weight with respect to 100 parts by weight of the component (A).
Vulcanization accelerating aid: Examples of the vulcanization accelerating aid include zinc oxide, activated zinc oxide, and magnesium oxide. One kind of those aids is used alone, or two or more kinds thereof are used in combination. Of those1 zinc oxide is preferred from the viewpoint of a balance among the storage stability, solvent stress cracking resistance, and permanent compression set property.
The content of the vulcanization accelerating aid is set within the range of typically 0.5 to parts by weight, preferably 3 to 10 parts by weight with respect to 100 parts by weight of the component (A).
Vulcanization retarder: Examples of the vulcanization retarder include N-(cyclohexylthio)phthalimide.
The content of the vulcanization retarder is set within the range of typically 0.1 to 5 parts by weight with respect to 100 parts by weight of the component (A).
Filler: Examples of the filler include calcium carbonate, magnesium carbonate, clay, talc, and mica. One kind of those fillers is used alone, or two or more kinds thereof are used in combination.
The content of the filler is set within the range of typically 10 to 200 parts by weight with respect to 100 parts by weight of the component (A).
The rubber composition of the present invention can be prepared by blending predetermined amounts of both TBZT and TOT-N (components (B)) in NBR-PVC or NBR (component (A)), optionally lurther blending carbon black, an antioxidant, and the like, and kneading the mixture using a kneading machine such as a kneader, a Banbury mixer, or a roll.
The rubber composition of the present invention may be used for at least one part (or for the whole) of an automobile fuel system part such as an automobile fuel delivery hose or an automobile fuel seal. Examples of the automobile fuel delivery hose include a filler neck tube, a breather hose, an evaporation hose, and a purge hose, which are brought into contact with a fuel (such as gasoline or gasoline steam). In addition, examples of the automobile fuel seal include a tank packing, a gasket, and an 0-ring, which are brought into contact with a fuel (such as gasoline or gasoline steam).
The automobile fuel delivery hose (hereinafter, appropriately abbreviated as "fuel delivery hose") of the present invention may be produced as follows, for example. A rubber composition prepared as above is molded by extrusion using an extrusion molding machine, and the molded product is steam-vulcanized (for example, 155°Cx20 minutes), to thereby obtain a fuel delivery hose having a monolayer structure. It should be noted that, if necessary, a mandrel may be used. In that case, a mold release agent such as a glycol-based mold release agent (such as polyethylene glycol (PEG), polypropylene glycol (PPG), or a mixture thereof) or a silicone emulsion-based mold release agent may be applied onto one or both of the inner peripheral surface of the hose and the outer peripheral surface of the mandrel.
The fuel delivery hose of the present invention may have not only the monolayer structure but also a multilayer structure obtained by forming at least one layer on the outer periphery of the monolayer structurt In addition, a reinforcing layer may be formed on at least one part of a hose having the multilayer structure.
In the fuel delivery hose of the present invention, the inner diameter of the hose preferably falls within the range of 2 to 100 mm, particularly preferably 5 to 50mm, and the thickness of the hose preferably falls within the range of 0.5 to 20 mm, particularly preferably 1 to 10mm.
I
Examples
Next, examples are described together with comparative examples. It should be noted that the present invention is not limited to these examples.
First, prior to the examples and the comparative examples, the following materials were prepared: NBR-PVC (component (A)) Nipol DN5OSSCR manufactured by ZEON CORPORATION (content of AN: 38.0%) Tetrabenzylthiuram disuffide (TBZT) (component (B)) Accel TBZT manufactured by Kawaguchi Chemical Industry Co., LTD.
Tetrabis(2-ethylhexyl)thiuram disulfide (TOT-N) (component (B)) Nocceler TOT-N manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.
Sulfenamide-based vulcanization accelerator (for comparative examples) N-cyclohexyl-2-benzothiazolesulfenamide (Accel CZ manufactured by Kawaguchi Chemical Industry Co., LTD.) Thiuram-based vulcanization accelerator (for comparative examples) Tetramethylthiuram disulfide (TMTD) (Accel TMT manufactured by Kawaguchi Chemical Industry Co., LTD.) Zinc oxide Zinc oxide type 2 manufactured by MITSUI MINING & SMELTING CO., LTD.
Processing aid Stearic acid (LUNAC S-70V manufactured by Kao Corporation) Antioxidant (i) Antage 3C manufactured by Kawaguchi Chemical Industry Co., LTD.
Antioxidant (ii) Antage RD manufactured by Kawaguchi Chemical Industry Co., LTD.
Carbon black SEAST V manufactured by Tokai Carbon Co., Ltd. Polyether-based plasticizer ADK CIZER R5107 manufactured byADEKA CORPORATION Vulcanizing agent Sulfur (manufactured by Tsurumi Chemical Industry Co., Ltd.) Examples Ito 6 and Comparative Examples I to 3 The components shown in Table 1 below were blended at ratios shown in the table, and the mixtures were kneaded using a 3 L-kneader to prepare rubber compositions. Next, the rubber compositions were extruded using an extrusion molding machine, and the resultant products were subjected to steam vulcanization (155°Cx20 minutes) to prepare fuel delivery hoses each having a monolayer structure (inner diameter: 30 mm, thickness: 3 mm).
Table I
(Part(s) by weight) Example Comparative Example 1 2 3 4 5 6 1 2 3 NBR-PVC 105* 105* 105* 105* 105 105* 105* 105* 105* AccelTBZT 3 2 4 4 4 4 -1.5 5 Nocceler 2 1 3 1 1 1 -1 -
TOT-N
AccelCZ ------1.5 -- AcceITMT ------1.5 --Zincoxicie 5 5 5 5 3 10 5 5 5 Processing 1 1 1 1 0.5 1.5 1 1 1 aid Antioxidant 2 2 2 2 2 2 2 2 2 (i) Antioxidant 2 2 2 2 2 2 2 2 2 (ii) Carbon 50 50 50 50 50 50 50 50 black Plasticizer 20 20 20 20 20 20 20 20 20 Vulcanizing 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 agent Storage 1.17 1.12 1.22 1_la 1.13 124 1.35 1.08 1.13 stability o o 0 0 ° I I 0 (Evaluation) I Solvent j 1 2 2 2 2 2 21 2 2 stress minute minutes minutes minutes minutes minutes minutes1 i minutes minutes cracking I and or more or more or more or more or more or more or more or more resistance I I second o o o 0 0 0 0 (Evaluation) I Permanent 52 55 48 J 53 49 55 50 63 57 compression I I set property I (Evaluation) ° ° ° ° ° ° I The rubber is oil extended NBR-PVC and thus contains 5 parts by weight of a plasticizer and parts by weight in terms of NBR-PVC.
The fuel delivery hoses thus obtained in the examples and comparative examples were used to evaluate characteristics in accordance with the following criteria. Table 1 above shows the results together.
Storage stability The rubber compositions were used to evaluate the storage stability in accordance with JIS K6300. That is, Mooney viscosities (ML1+3, 125°C) at the initial time (untreated) and after heat aging (40°Cx72 hours) were measured to evaluate the storage stability as follows.
Evaluation a: The value of (Mooney viscosity after dry aging/Mooney viscosity at the initial time) is less than 1.25.
: The value of (Mooney viscosity after heat aging/Mooney viscosity at the initial time) is 1.25 or more.
Solvent stress cracking resistance A notch (2.5 mm) was made at the center of a JIS No.1 dumbbell cut out from each hose. The dumbbell was immersed in a fuel liquid (Fuel C) and left to stand in a 40°C environment, and a time until the dumbbell was broken was measured.
Evaluation c: The time until the dumbbell is broken is 2 minutes or more.
: The time until the dumbbell is broken is less than 2 minutes.
Permanent compression set property Each rubber composition was used to prepare a large test piece (thickness: 12.5±0.5 mm, diameter: 29.0±0.5 mm), and the permanent compression set property was evaluated in accordance with JIS K 6262 at a temperature of 100°C for a test time of 72 hours at a compressibility of 25%.
Evaluation 0: The permanent compression set property is 55% or less.
K: The permanent compression set property exceeds 55%, As can be seen from the results of Table 1 above, the compositionè of Exarriples 1 to 6 were found to have excellent storage stability, solvent stress cracking resistance, and permanent compression set property because the compositions contained predetermined amounts of TBZT and TOT-N only as specific vulcanization accelerators (components (BD.
On the other hand, the compositions of Comparative Examples ito 3 were found to be inferior in any of the storage stability, solvent stress cracking resistance, and permanent compression set property.
it should be noted that specific embodiments in the present invention are shown in the above-mentioned examples, but the examples are to be considered as merely illustrative and not restrictive. In addition, all changes of the scope of the invention which come within the meaning and scope of equivalency of the claims are intended to be embraced thereby.
Industrial Applicability
The rubber composition of the present invention is used for an automobile fuel system part such as an automobile fuel delivery hose or an automobile fuel seal. Examples of the automobile fuel delivery hose include a filler neck tube, a breather hose, an evaporation hose, and a purge hose, which are brought into contact with a fuel (such as gasoline or gasoline steam).
In addition, examples of the automobile fuel seal include a tank packing, a gasket, and an 0-ring, which are brought into contact with a fuel (such as gasoline or gasoline steam).
Claims (5)
- CLAIMS1. A rubber composition for use in an automobile fuel system part, comprising: component (A) as a main component: and components (B) only as vulcanization accelerators, wherein the content of the components (B) exceeds 2.5 parts by weight with respect to parts by weight of the component (A); and component (A) consists of either acrylonitrile-butadiene rubber ora blended rubber of acrylonitrile-butacliene and polyvinyl chloride * and components (B) is a mixture of tetrabenzylthiuram disulfide (TBZT) and tetrabis(2-ethylhexyl)thiuram disulfide (TOT-N).
- 2. A rubber composition according to claim 1, wherein the mixing ratio by weight of TBZT (81) to TOT-N (92) in the components (B) falls within the range of 81/92=99/1 to 50/50.
- 3. A rubber composition according to claim 1 or 2, further comprising stearic acid and zinc oxide, wherein the content of the stearic acid is 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the component (A), and the content of the zinc oxide is 3 to 10 parts by weight with respect to 100 parts by weight of the component (A).
- 4. An automobile fuel system part, comprising the rubber composition according to any one of claims ito 3,
- 5. An automobile fuel system part according to claim 4, wherein the automobile fuel system part is an automobile fuel delivery hose or an automobile fuel seal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011006045 | 2011-01-14 | ||
| PCT/JP2011/070463 WO2012096031A1 (en) | 2011-01-14 | 2011-09-08 | Rubber composition and automobile fuel system part using same |
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| GB201304367D0 GB201304367D0 (en) | 2013-04-24 |
| GB2501173A true GB2501173A (en) | 2013-10-16 |
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| JP (1) | JP5655096B2 (en) |
| CN (1) | CN103249772B (en) |
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| JP6357768B2 (en) * | 2013-12-26 | 2018-07-18 | ダイキン工業株式会社 | Laminate |
| CN105273329A (en) * | 2014-06-25 | 2016-01-27 | 苏州辛帝斯燃气密封材料有限公司 | Domestic gas hose, processing process thereof and special-purposed production device thereof |
| CN104592589B (en) * | 2015-01-01 | 2016-10-05 | 宁波帝杨电子科技有限公司 | A kind of nitrile rubber/polyvinyl chloride composite materials and preparation method thereof |
| JP6761718B2 (en) * | 2016-09-30 | 2020-09-30 | 住友理工株式会社 | How to make a hose |
| CN107474436A (en) * | 2017-08-31 | 2017-12-15 | 徐州市恒基伟业建材发展有限公司 | A kind of plastic formula for being used to make automotive oil tank |
| JP2019199549A (en) * | 2018-05-16 | 2019-11-21 | Nok株式会社 | Rubber composition and seal material |
| CN113896963A (en) * | 2021-11-25 | 2022-01-07 | 南阳天一密封股份有限公司 | Rubber sealing material for mixed fuel bearing system and preparation process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072804A (en) * | 1999-06-28 | 2001-03-21 | Tokai Rubber Ind Ltd | Rubber composition and fuel delivery hose for automobile |
| JP2001317663A (en) * | 2000-05-11 | 2001-11-16 | Tokai Rubber Ind Ltd | Fuel transportation hose |
| WO2007145026A1 (en) * | 2006-06-16 | 2007-12-21 | Nok Corporation | Rubber-metal laminate |
| JP2008239832A (en) * | 2007-03-28 | 2008-10-09 | Jsr Corp | Rubber composition, crosslinked rubber and molded product |
| JP2009001657A (en) * | 2007-06-21 | 2009-01-08 | Yokohama Rubber Co Ltd:The | Adhesive rubber composition for hose |
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| JP5096764B2 (en) * | 2007-02-27 | 2012-12-12 | 東海ゴム工業株式会社 | Non-aqueous hose for automobile |
| JP2010155883A (en) * | 2008-12-26 | 2010-07-15 | Nippon Zeon Co Ltd | Nitrile copolymer rubber composition |
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- 2011-09-08 WO PCT/JP2011/070463 patent/WO2012096031A1/en active Application Filing
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072804A (en) * | 1999-06-28 | 2001-03-21 | Tokai Rubber Ind Ltd | Rubber composition and fuel delivery hose for automobile |
| JP2001317663A (en) * | 2000-05-11 | 2001-11-16 | Tokai Rubber Ind Ltd | Fuel transportation hose |
| WO2007145026A1 (en) * | 2006-06-16 | 2007-12-21 | Nok Corporation | Rubber-metal laminate |
| JP2008239832A (en) * | 2007-03-28 | 2008-10-09 | Jsr Corp | Rubber composition, crosslinked rubber and molded product |
| JP2009001657A (en) * | 2007-06-21 | 2009-01-08 | Yokohama Rubber Co Ltd:The | Adhesive rubber composition for hose |
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| Publication number | Publication date |
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| GB2501173A8 (en) | 2015-11-11 |
| WO2012096031A1 (en) | 2012-07-19 |
| JP5655096B2 (en) | 2015-01-14 |
| JPWO2012096031A1 (en) | 2014-06-09 |
| CN103249772A (en) | 2013-08-14 |
| GB201304367D0 (en) | 2013-04-24 |
| CN103249772B (en) | 2014-12-17 |
| GB2501173B (en) | 2017-06-14 |
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