JP5655096B2 - Rubber composition and automobile fuel member using the same - Google Patents
Rubber composition and automobile fuel member using the same Download PDFInfo
- Publication number
- JP5655096B2 JP5655096B2 JP2012552625A JP2012552625A JP5655096B2 JP 5655096 B2 JP5655096 B2 JP 5655096B2 JP 2012552625 A JP2012552625 A JP 2012552625A JP 2012552625 A JP2012552625 A JP 2012552625A JP 5655096 B2 JP5655096 B2 JP 5655096B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- parts
- rubber composition
- nbr
- 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.)
- Active
Links
- 239000000446 fuel Substances 0.000 title claims description 49
- 229920001971 elastomer Polymers 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 title claims description 38
- 239000005060 rubber Substances 0.000 title claims description 38
- 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 description 34
- 238000004073 vulcanization Methods 0.000 claims description 33
- 229920000459 Nitrile rubber Polymers 0.000 claims description 28
- 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 description 24
- 239000004800 polyvinyl chloride Substances 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 21
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 20
- 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
- -1 2-ethylhexyl Chemical group 0.000 claims description 7
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 description 19
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 229960002447 thiram Drugs 0.000 description 17
- 230000006835 compression Effects 0.000 description 16
- 238000007906 compression Methods 0.000 description 16
- 238000003860 storage Methods 0.000 description 16
- 239000003502 gasoline Substances 0.000 description 12
- 230000003712 anti-aging effect Effects 0.000 description 11
- 239000004014 plasticizer Substances 0.000 description 10
- 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
- 230000001133 acceleration Effects 0.000 description 3
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 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
- 238000005336 cracking Methods 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
- 239000002671 adjuvant Substances 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
- 230000000638 stimulation Effects 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
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)
Description
本発明は、自動車用燃料部材に用いられるゴム組成物およびそれを用いた自動車用燃料部材に関するものであり、詳しくは燃料（ガソリン、ガソリン蒸気等）と接触する、フィラーネックチューブ，ブリーザーホース，エバポレーションホース，パージホース等の自動車用燃料輸送ホースや、燃料（ガソリン、ガソリン蒸気等）と接触する、タンクパッキン，ガスケット，Ｏ−リング等の自動車用燃料シールに用いられるゴム組成物およびそれを用いた自動車用燃料部材に関するものである。 TECHNICAL FIELD 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.). Rubber composition used for automotive 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.
従来から、自動車用燃料輸送ホース等の自動車用燃料部材に用いられるゴム組成物としては、アクリロニトリル−ブタジエンゴム（ＮＢＲ）とポリ塩化ビニル（ＰＶＣ）とのブレンドゴム（ＮＢＲ−ＰＶＣ）、またはＮＢＲを主成分とし、これにテトラメチルチウラムジスルフィド（ＴＭＴＤ）等の低分子量のチウラム系加硫促進剤や、スルフェンアミド系加硫促進剤を配合したものが使用されている（特許文献１〜４参照）。 Conventionally, as 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. As a main component, 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). ).
しかしながら、上記ＴＭＴＤ等の低分子量のチウラム系加硫促進剤やスルフェンアミド系加硫促進剤は、反応活性が高く、ゴム未加硫時の貯蔵安定性が劣るとともに、加硫密度が密になるため、燃料油に浸漬した際に亀裂が生じやすく、耐ソルベントクラック性（ソルベントクラックの発生を抑制する性能）に劣るという難点がある。一方、上記ＴＭＴＤ等の低分子量のチウラム系加硫促進剤やスルフェンアミド系加硫促進剤の含有量を減らすと、上記貯蔵安定性や耐ソルベントクラック性は向上するが、圧縮永久歪性が劣るという新たな課題が発生することになる。 However, 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 | occurrence | production of a solvent crack). On the other hand, when 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.
本発明は、このような事情に鑑みなされたもので、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性の全ての性能に優れた、ゴム組成物およびそれを用いた自動車用燃料部材の提供をその目的とする。 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.
上記の目的を達成するため、本発明は、自動車用燃料部材に用いられるゴム組成物であって、下記の（Ａ）を主成分とし、加硫促進剤として下記の（Ｂ）成分のみを含有し、上記（Ｂ）成分の含有量が、上記（Ａ）成分１００重量部に対して２．５重量部を超え７重量部以下であるゴム組成物を第１の要旨とする。
（Ａ）アクリロニトリル−ブタジエンゴム（ＮＢＲ）とポリ塩化ビニル（ＰＶＣ）とのブレンドゴム（ＮＢＲ−ＰＶＣ）、またはＮＢＲ。
（Ｂ）テトラベンジルチウラムジスルフィド（ＴＢＺＴ）、およびテトラビス（２−エチルヘキシル）チウラムジスルフィド（ＴＯＴ−Ｎ）の双方。
In order to achieve the above object, the present invention is a rubber composition used for a fuel member for automobiles, comprising the following (A) as a main component and only the following component (B) as a vulcanization accelerator. and the content of the component (B), the above (a) 2.5 parts by weight exceeds 7 parts by weight or less der Ru rubber composition of the component 100 parts by weight of the first aspect.
(A) A blend 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).
また、本発明は、上記ゴム組成物を、自動車用燃料部材の少なくとも一部に用いてなる自動車用燃料部材を第２の要旨とする。 Moreover, this invention makes the 2nd summary the fuel member for motor vehicles which uses the said rubber composition for at least one part of the fuel member for motor vehicles.
すなわち、本発明者は、テトラメチルチウラムジスルフィド（ＴＭＴＤ）等の低分子量のチウラム系加硫促進剤やスルフェンアミド系加硫促進剤に代わる、加硫促進剤について鋭意研究を重ねた。その研究の過程で、チウラム系加硫促進剤のなかでも、高分子量であるテトラベンジルチウラムジスルフィド（ＴＢＺＴ）およびテトラビス（２−エチルヘキシル）チウラムジスルフィド（ＴＯＴ−Ｎ）に着目し、このＴＢＺＴおよびＴＯＴ−Ｎのみを加硫促進剤として使用すると、反応活性の高さを解消でき、加硫開始のスピードが遅くなり、ゴム未加硫時の貯蔵安定性に優れるとともに、加硫密度が密になりにくいため、燃料油に浸漬した際に亀裂発生を抑制でき、耐ソルベントクラック性が向上することを突き止めた。そして、上記ＴＢＺＴおよびＴＯＴ−Ｎの含有量を、ＮＢＲ−ＰＶＣまたはＮＢＲ１００重量部に対して２．５重量部を超え７重量部以下に設定すると、貯蔵安定性および耐ソルベントクラック性の両者の性能を低下させることなく、圧縮永久歪性が向上し、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性の全ての性能に優れたゴム組成物が得られることを見いだし、本発明に到達した。 That is, the present inventor has conducted extensive research on vulcanization accelerators in place of low molecular weight thiuram vulcanization accelerators and sulfenamide vulcanization accelerators such as tetramethylthiuram disulfide (TMTD). In the course of the research, among the thiuram vulcanization accelerators, attention was paid to tetrabenzylthiuram disulfide (TBZT) and tetrabis (2-ethylhexyl) thiuram disulfide (TOT-N), which are high molecular weights. When only N is used as a vulcanization accelerator, the high reaction activity can be eliminated, the speed of vulcanization start is slowed, the storage stability when rubber is not vulcanized is excellent, and the vulcanization density is difficult to become dense. Therefore, it was found that cracking can be suppressed when immersed in fuel oil, and the resistance to solvent cracking is improved. And when content of the said TBZT and TOT-N is set to more than 2.5 weight part and 7 weight part or less with respect to 100 weight part of NBR-PVC or NBR, both performance of storage stability and solvent crack resistance The present inventors have found that a rubber composition having improved compression set properties and excellent storage stability, solvent crack resistance, and compression set properties can be obtained without lowering the viscosity.
以上のように、本発明の自動車用燃料部材に用いられるゴム組成物（以下、単に「ゴム組成物」という場合もある。）は、加硫促進剤としてテトラベンジルチウラムジスルフィド（ＴＢＺＴ）およびテトラビス（２−エチルヘキシル）チウラムジスルフィド（ＴＯＴ−Ｎ）のみを含有し、上記ＴＢＺＴおよびＴＯＴ−Ｎの双方（Ｂ成分）〔以下、単に「ＴＢＺＴおよびＴＯＴ−Ｎ（Ｂ成分）」と略す場合もある〕の含有量が、ＮＢＲ−ＰＶＣまたはＮＢＲ（Ａ成分）１００重量部に対して２．５重量部を超え７重量部以下に設定されているため、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性の全ての性能に優れるという効果が得られる。 As described above, 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. 2-ethylhexyl) thiuram disulfide (TOT-N) only, and both TBZT and TOT-N (component B) [hereinafter sometimes simply referred to as “TBZT and TOT-N (component B)]” Since the content is set to more than 2.5 parts by weight and not more than 7 parts by weight with respect to 100 parts by weight of NBR-PVC or NBR (component A), storage stability, solvent crack resistance, compression set resistance The effect that it is excellent in all the performances of is obtained.
また、上記Ｂ成分中のＴＢＺＴ（Ｂ１）と、ＴＯＴ−Ｎ（Ｂ２）との重量混合比が、Ｂ１／Ｂ２＝９９／１〜５０／５０の範囲であると、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性の全ての性能のバランスが良好となる。 Further, when the weight mixing ratio of TBZT (B1) and TOT-N (B2) in the component B is in the range of B1 / B2 = 99/1 to 50/50, storage stability and solvent crack resistance The balance of performance and compression set properties is good.
また、本発明のゴム組成物が、上記Ａ成分およびＢ成分に加えて、さらにステアリン酸および酸化亜鉛を含有し、上記ステアリン酸の含有量が上記Ａ成分１００重量部に対して０．５〜１．５重量部、上記酸化亜鉛の含有量が上記Ａ成分１００重量部に対して３〜１０重量部である場合には、上記Ｂ成分の分解物と酸化亜鉛との反応よりも、ステアリン酸と酸化亜鉛との反応が優先するため、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性のバランスがより良好となる。 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. When the content of zinc oxide is 3 to 10 parts by weight with respect to 100 parts by weight of component A, stearic acid is used rather than the reaction between the decomposition product of 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.
そして、本発明のゴム組成物を少なくとも一部（全部であっても差し支えない）に用いてなる自動車用燃料部材（自動車用燃料輸送ホースまたは自動車用燃料シール）は、燃料油に浸漬した際の亀裂発生を抑制できることから、耐ソルベントクラック性に優れている。 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.
つぎに、本発明の実施の形態について詳しく説明する。ただし、本発明は、この実施の形態に限られるものではない。 Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to this embodiment.
本発明の自動車用燃料部材に用いるゴム組成物は、アクリロニトリル−ブタジエンゴム（ＮＢＲ）とポリ塩化ビニル（ＰＶＣ）とのブレンドゴム（ＮＢＲ−ＰＶＣ）またはＮＢＲ（Ａ成分）と、テトラベンジルチウラムジスルフィド（ＴＢＺＴ）およびテトラビス（２−エチルヘキシル）チウラムジスルフィド（ＴＯＴ−Ｎ）の双方（Ｂ成分）とを用いて得ることができる。本発明においては、加硫促進剤として上記ＴＢＺＴおよびＴＯＴ−Ｎのみを含有し、上記ＴＢＺＴおよびＴＯＴ−Ｎの双方（Ｂ成分）の含有量が、ＮＢＲ−ＰＶＣまたはＮＢＲ（Ａ成分）１００重量部に対して、２．５重量部を超え７重量部以下に設定されている。これが、本発明の最大の特徴である。 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), tetrabenzylthiuram disulfide ( TBZT) and tetrabis (2-ethylhexyl) thiuram disulfide (TOT-N) (B component). In the present invention, only TBZT and TOT-N are contained as a vulcanization accelerator, and the contents of both TBZT and TOT-N (component B) are NBR-PVC or NBR (component A) 100 parts by weight. On the other hand, it is set to more than 2.5 parts by weight and 7 parts by weight or less . This is the greatest feature of the present invention.
つぎに、これらの成分について説明する。
《ＮＢＲ−ＰＶＣまたはＮＢＲ（Ａ成分）》
上記ＮＢＲ−ＰＶＣにおける、ＮＢＲとＰＶＣとのブレンド比（重量比）は、耐オゾン性の点から、ＮＢＲ／ＰＶＣ＝８５／１５〜６５／３５の範囲が好ましく、特に好ましくはＮＢＲ／ＰＶＣ＝８０／２０〜７０／３０の範囲である。Next, these components will be described.
<< NBR-PVC or NBR (A component) >>
In the NBR-PVC, the blend ratio (weight ratio) of NBR and PVC is preferably in the range of NBR / PVC = 85/15 to 65/35, particularly preferably NBR / PVC = 80, from the viewpoint of ozone resistance. / 20 to 70/30.
上記ＮＢＲとしては、耐燃料バリア性と低温性のバランスの点から、アクリロニトリル（ＡＮ）量が２５〜６５％の範囲のものが好ましく、特に好ましくはＡＮ量が３０〜６０％の範囲である。 The NBR preferably has an acrylonitrile (AN) content in the range of 25 to 65%, particularly preferably an AN content in the range of 30 to 60%, from the viewpoint of the balance between fuel barrier properties and low temperature properties.
なお、本発明においては、上記ＮＢＲと共重合可能なモノマーを配合しても差し支えない。 In the present invention, a monomer copolymerizable with the NBR may be blended.
また、上記ＰＶＣは、平均重合度が７００〜１４００の範囲のものが好ましく、特に好ましくは８００前後のものである。 The PVC preferably has an average degree of polymerization in the range of 700 to 1400, particularly preferably around 800.
本発明のゴム組成物におけるＡ成分としては、耐オゾン性の点から、ＮＢＲ単体よりも、ＮＢＲにＰＶＣをブレンドしたＮＢＲ−ＰＶＣの方が好ましい。 As the component A in the rubber composition of the present invention, NBR-PVC in which PVC is blended with NBR is preferable to NBR alone from the viewpoint of ozone resistance.
なお、本発明において、Ａ成分を主成分とするとは、本発明のゴム組成物においてＡ成分が主要成分であるとの意味である。 In the present invention, the phrase “component A as a main component” means that the component A is a main component in the rubber composition of the present invention.
《ＴＢＺＴおよびＴＯＴ−Ｎの双方（Ｂ成分）》
本発明のゴム組成物においては、加硫促進剤として、上記ＴＢＺＴおよびＴＯＴ−Ｎのみを使用し、テトラメチルチウラムジスルフィド（ＴＭＴＤ）等のチウラム系加硫促進剤や、スルフェンアミド系加硫促進剤を含有しない。<< both TBZT and TOT-N (B component) >>
In the rubber composition of the present invention, only TBZT and TOT-N are used as vulcanization accelerators, and thiuram vulcanization accelerators such as tetramethylthiuram disulfide (TMTD) and sulfenamide vulcanization accelerators are used. Contains no agent.
本発明において、上記ＴＢＺＴおよびＴＯＴ−Ｎの双方（Ｂ成分）の総含有量は、上記ＮＢＲ−ＰＶＣまたはＮＢＲ（Ａ成分）１００重量部に対して２．５重量部を超え７重量部以下であり、最も好ましくは５〜７重量部の範囲である。すなわち、上記Ｂ成分の含有量が少なすぎると、圧縮永久歪性が劣るからである。 In the present invention, the total content of both TBZT and TOT-N (component B) is more than 2.5 parts by weight and not more than 7 parts by weight with respect to 100 parts by weight of the NBR-PVC or NBR (component A). Ah it is, most preferably in the range of 5-7 parts by weight. That is, if the content of the component B is too small, the compression set is inferior.
上記Ｂ成分中のＴＢＺＴ（Ｂ１）と、ＴＯＴ−Ｎ（Ｂ２）との重量混合比は、Ｂ１／Ｂ２＝９９／１〜５０／５０の範囲が好ましく、特に好ましくはＢ１／Ｂ２＝９０／１０〜５５／４５の範囲が好ましく、最も好ましくはＢ１／Ｂ２＝８０／２０〜６０／４０の範囲である。すなわち、ＴＢＺＴ（Ｂ１）の混合比が大きすぎる〔ＴＯＴ−Ｎ（Ｂ２）の混合比が小さすぎる〕と、架橋が不充分となり圧縮永久歪性が低下する傾向があり、逆にＴＢＺＴ（Ｂ１）の混合比が小さすぎる〔ＴＯＴ−Ｎ（Ｂ２）の混合比が大きすぎる〕と、耐ソルベントクラック性が低下する傾向がみられるからである。 The weight mixing ratio of TBZT (B1) and TOT-N (B2) in the component B is preferably in the range of B1 / B2 = 99/1 to 50/50, particularly preferably B1 / B2 = 90/10. The range of ˜55 / 45 is preferable, and the range of B1 / B2 = 80/20 to 60/40 is most preferable. That is, if the mixing ratio of TBZT (B1) is too large [the mixing ratio of TOT-N (B2) is too small], the crosslinking tends to be insufficient and the compression set tends to be reduced. Conversely, TBZT (B1) This is because if the mixing ratio is too small (the mixing ratio of TOT-N (B2) is too large), the solvent crack resistance tends to decrease.
なお、本発明のゴム組成物には、上記ＮＢＲ−ＰＶＣまたはＮＢＲ（Ａ成分）および特定の加硫促進剤（Ｂ成分）に加えて、加工助剤、老化防止剤、補強剤、可塑剤、加硫剤、加硫促進助剤、加硫遅延剤、白色充填剤、着色剤等を必要に応じて適宜配合しても差し支えない。 In addition to the NBR-PVC or NBR (component A) and the specific vulcanization accelerator (component B), the rubber composition of the present invention includes a processing aid, an anti-aging agent, a reinforcing agent, a plasticizer, Vulcanizing agents, vulcanization accelerating aids, vulcanization retarders, white fillers, colorants and the like may be appropriately blended as necessary.
《加工助剤》
加工助剤としては、例えば、ステアリン酸、脂肪酸エステル、脂肪酸アミド、炭化水素樹脂等があげられ、単独でもしくは二種以上併せて用いられる。これらのなかでも、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性のバランスの点から、ステアリン酸が好ましい。《Processing aid》
Examples of 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. Among these, stearic acid is preferable from the viewpoint of the balance between storage stability, solvent crack resistance, and compression set.
上記加工助剤の含有量は、上記ＮＢＲ−ＰＶＣまたはＮＢＲ（Ａ成分）１００重量部に対して、通常、０．１〜１０重量部の範囲に設定され、好ましくは０．５〜１．５重量部の範囲である。 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.
《老化防止剤》
老化防止剤としては、例えば、フェニレンジアミン系老化防止剤、フェノール系老化防止剤、ジフェニルアミン系老化防止剤、キノリン系老化防止剤、ワックス類等があげられ、単独でもしくは二種以上併せて用いられる。《Anti-aging agent》
Examples of the anti-aging agent 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. .
上記老化防止剤の含有量は、上記Ａ成分１００重量部に対して、通常、０．１〜１０重量部の範囲に設定される。 The content of the anti-aging agent is usually set in a range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the component A.
《補強剤》
補強剤としては、例えば、カーボンブラック、シリカ等があげられ、単独でもしくは二種以上併せて用いられる。《Reinforcing agent》
Examples of the reinforcing agent include carbon black, silica and the like, and they are used alone or in combination of two or more.
上記カーボンブラックとしては、例えば、ＳＡＦ級、ＩＳＡＦ級、ＨＡＦ級、ＭＡＦ級、ＦＥＦ級、ＧＰＦ級、ＳＲＦ級、ＦＴ級、ＭＴ級等のグレードのものがあげられる。これらは単独でもしくは二種以上併せて用いられる。 Examples of the carbon black include SAF class, ISAF class, HAF class, MAF class, FEF class, GPF class, SRF class, FT class, and MT class grades. These may be used alone or in combination of two or more.
上記補強剤の含有量は、上記Ａ成分１００重量部に対して、通常、１０〜２００重量部の範囲に設定される。 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.
《可塑剤》
可塑剤としては、例えば、フタル酸ジ−２−エチルヘキシル（ＤＯＰ），フタル酸ジ−ｎ−ブチル（ＤＢＰ）等のフタル酸系可塑剤、ジブチルカルビトールアジペート，ジオクチルアジペート（ＤＯＡ）等のアジピン酸系可塑剤、セバシン酸ジオクチル（ＤＯＳ），セバシン酸ジブチル（ＤＢＳ）等のセバシン酸系可塑剤、トリクレジルフォスフェート（ＴＣＰ）等のフォスフェート系可塑剤、ポリエーテル系可塑剤等があげられる。これらは単独でもしくは二種以上併せて用いられる。《Plasticizer》
Examples of the plasticizer 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.
上記可塑剤の含有量は、上記Ａ成分１００重量部に対して、通常、５〜１００重量部の範囲に設定される。 Content of the said plasticizer is normally set to the range of 5-100 weight part with respect to 100 weight part of said A component.
《加硫剤》
加硫剤としては、例えば、硫黄、モルホリン、ジスルフィド等の硫黄化合物、有機過酸化物等があげられ、単独でもしくは二種以上併せて用いられる。《Vulcanizing agent》
Examples of the vulcanizing agent 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.
上記加硫剤の含有量は、上記Ａ成分１００重量部に対して、通常、０．２〜５重量部の範囲に設定される。 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.
《加硫促進助剤》
加硫促進助剤としては、例えば、酸化亜鉛、活性亜鉛華、酸化マグネシウム等があげられ、単独でもしくは二種以上併せて用いられる。これらのなかでも、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性のバランスの点から、酸化亜鉛が好ましい。《Vulcanization acceleration aid》
Examples of the vulcanization acceleration aid 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.
上記加硫促進助剤の含有量は、上記Ａ成分１００重量部に対して、通常、０．５〜１０重量部の範囲に設定され、好ましくは３〜１０重量部の範囲である。 Content of the said vulcanization | cure acceleration | stimulation adjuvant is normally set to the range of 0.5-10 weight part with respect to 100 weight part of said A component, Preferably it is the range of 3-10 weight part.
《加硫遅延剤》
加硫遅延剤としては、例えば、Ｎ−（シクロヘキシルチオ）フタルイミド等があげられる。《Vulcanization retarder》
Examples of the vulcanization retarder include N- (cyclohexylthio) phthalimide.
上記加硫遅延剤の含有量は、上記Ａ成分１００重量部に対して、通常、０．１〜５重量部の範囲に設定される。 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.
《充填剤》
充填剤としては、例えば、炭酸カルシウム、炭酸マグネシウム、クレー、タルク、マイカ等があげられ、単独でもしくは二種以上併せて用いられる。"filler"
Examples of the filler include calcium carbonate, magnesium carbonate, clay, talc, mica and the like, and they are used alone or in combination of two or more.
上記充填剤の含有量は、上記Ａ成分１００重量部に対して、通常、１０〜２００重量部の範囲に設定される。 Content of the said filler is normally set to the range of 10-200 weight part with respect to 100 weight part of said A component.
本発明のゴム組成物は、上記ＮＢＲ−ＰＶＣまたはＮＢＲ（Ａ成分）に、所定量のＴＢＺＴおよびＴＯＴ−Ｎの双方（Ｂ成分）を配合し、さらに必要に応じてカーボンブラック、老化防止剤等を配合し、これらをニーダー、バンバリーミキサー、ロール等の混練機を用いて混練することにより調製することができる。 In the rubber composition of the present invention, a predetermined amount of both TBZT and TOT-N (component B) is blended with the NBR-PVC or NBR (component A), and carbon black, an anti-aging agent, etc., if necessary. And kneading them using a kneader such as a kneader, a Banbury mixer, or a roll.
本発明のゴム組成物は、自動車用燃料輸送ホースや、自動車用燃料シール等の自動車用燃料部材の少なくとも一部（全部であっても差し支えない）に用いられる。上記自動車用燃料輸送ホースとしては、例えば、燃料（ガソリン、ガソリン蒸気等）と接触する、フィラーネックチューブ、ブリーザーホース、エバポレーションホース、パージホース等があげられる。また、上記自動車用燃料シールとしては、例えば、燃料（ガソリン、ガソリン蒸気等）と接触する、タンクパッキン、ガスケット、Ｏ−リング等があげられる。 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. Examples of 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 fuel seal for automobiles include tank packing, gaskets, O-rings, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
本発明の自動車用燃料輸送ホース（以下、適宜「燃料輸送ホース」と略す）は、例えば、つぎのようにして作製することができる。すなわち、上記のようにして調製したゴム組成物を、押出成形機を用いて押出成形し、これを蒸気加硫（例えば、１５５℃×２０分間）して、単層構造の燃料輸送ホースを得ることができる。なお、必要に応じて、マンドレルを使用しても差し支えない。この場合、ホースの内周面，マンドレルの外周面のいずれかもしくは双方に、グリコール系離型剤〔例えば、ポリエチレングリコール（ＰＥＧ）、ポリプロピレングリコール（ＰＰＧ）およびこれらの混合物〕、シリコーンエマルジョン系離型剤等の離型剤を塗布しても差し支えない。 The fuel transport hose for automobiles 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. In this case, 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.
本発明の燃料輸送ホースは、単層構造に限定されるものではなく、その外周に少なくとも１つの層を形成した多層構造であっても差し支えなく、また、上記多層構造のホースの一部に補強層を形成しても差し支えない。 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.
本発明の燃料輸送ホースにおいて、ホース内径は２〜１００ｍｍの範囲が好ましく、特に好ましくは５〜５０ｍｍの範囲であり、ホース肉厚は０．５〜２０ｍｍの範囲が好ましく、特に好ましくは１〜１０ｍｍの範囲である。 In the fuel transport hose of the present invention, 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.
つぎに、実施例について比較例と併せて説明する。ただし、本発明はこれら実施例に限定されるものではない。 Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.
まず、実施例および比較例に先立ち、下記に示す材料を準備した。 First, prior to the examples and comparative examples, the following materials were prepared.
〔ＮＢＲ−ＰＶＣ（Ａ成分）〕
日本ゼオン社製、ニポールＤＮ５０８ＳＣＲ（ＡＮ量：３８．０％）[NBR-PVC (component A)]
Nipol DN508SCR (AN amount: 38.0%) manufactured by Nippon Zeon
〔テトラベンジルチウラムジスルフィド（ＴＢＺＴ）（Ｂ成分）〕
川口化学工業社製、アクセルＴＢＺＴ[Tetrabenzylthiuram disulfide (TBZT) (component B)]
Accelerator TBZT, manufactured by Kawaguchi Chemical Co., Ltd.
〔テトラビス（２−エチルヘキシル）チウラムジスルフィド（ＴＯＴ−Ｎ）（Ｂ成分）〕
大内新興化学工業社製、ノクセラーＴＯＴ−Ｎ[Tetrabis (2-ethylhexyl) thiuram disulfide (TOT-N) (component B)]
Nouchira TOT-N, manufactured by Ouchi Shinsei Chemical Co., Ltd.
〔スルフェンアミド系加硫促進剤（比較例用）〕
Ｎ−シクロヘキシル−２−ベンゾチアゾールスルフェンアミド（川口化学工業社製、アクセルＣＺ）[Sulfenamide vulcanization accelerator (for comparative example)]
N-cyclohexyl-2-benzothiazole sulfenamide (manufactured by Kawaguchi Chemical Co., Ltd., Accel CZ)
〔チウラム系加硫促進剤（比較例用）〕
テトラメチルチウラムジスルフィド（ＴＭＴＤ）（川口化学工業社製、アクセルＴＭＴ）[Thiuram vulcanization accelerator (for comparative example)]
Tetramethylthiuram disulfide (TMTD) (manufactured by Kawaguchi Chemical Industries, Accel TMT)
〔酸化亜鉛〕
三井金属鉱業社製、酸化亜鉛２種[Zinc oxide]
2 types of zinc oxide manufactured by Mitsui Mining & Smelting Co., Ltd.
〔加工助剤〕
ステアリン酸（花王社製、ルナックＳ−７０Ｖ）[Processing aid]
Stearic acid (manufactured by Kao Corporation, Lunac S-70V)
〔老化防止剤(i)〕
川口化学工業社製、アンテージ３Ｃ
〔老化防止剤(ii)〕
川口化学工業社製、アンテージＲＤ(Anti-aging agent (i))
ANTAGE 3C, manufactured by Kawaguchi Chemical Co., Ltd.
(Anti-aging agent (ii))
ANTAGE RD, manufactured by Kawaguchi Chemical Co., Ltd.
〔カーボンブラック〕
東海カーボン社製、シーストＶ〔Carbon black〕
Toast Carbon Co., Ltd., Seast V
〔ポリエーテル系可塑剤〕
ＡＤＥＫＡ社製、アデカサイザーＲＳ１０７[Polyether plasticizer]
Made by ADEKA, Adeka Sizer RS107
〔加硫剤〕
硫黄（鶴見化学工業社製）[Vulcanizing agent]
Sulfur (made by Tsurumi Chemical Co., Ltd.)
〔実施例１〜６、比較例１〜３〕
下記の表１に示す各成分を同表に示す割合で配合し、３Ｌニーダーを用いて混練してゴム組成物を調製した。つぎに、上記ゴム組成物を押出成形機により押し出し、これを蒸気加硫（１５５℃×２０分間）して、単層構造の燃料輸送ホースを作製した（内径３０ｍｍ、厚み３ｍｍ）。[Examples 1-6, Comparative Examples 1-3]
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).
このようにして得られた実施例および比較例の燃料輸送ホースを用いて、下記の基準に従って、各特性の評価を行った。これらの結果を、上記表１に併せて示した。 Using the fuel transport hoses of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the following criteria. These results are also shown in Table 1 above.
〔貯蔵安定性〕
各ゴム組成物を用い、ＪＩＳ Ｋ６３００に準拠して貯蔵安定性の評価を行った。すなわち、初期（未処理）および乾熱老化後（４０℃×７２時間）のそれぞれのムーニー粘度（ＭＬ1+3、１２５℃）を測定し、以下のようにして貯蔵安定性の評価を行った。
〈評価〉
○：〔乾燥老化後のムーニー粘度／初期のムーニー粘度〕が１．２５未満のもの
×：〔乾燥老化後のムーニー粘度／初期のムーニー粘度〕が１．２５以上のもの[Storage stability]
Using each rubber composition, storage stability was evaluated according to JIS K6300. That is, the Mooney viscosities (ML 1 + 3 , 125 ° C.) at the initial stage (untreated) and after dry heat aging (40 ° C. × 72 hours) were measured, and the storage stability was evaluated as follows. .
<Evaluation>
○: [Mooney viscosity after dry aging / initial Mooney viscosity] is less than 1.25 x: [Mooney viscosity after dry aging / initial Mooney viscosity] is 1.25 or more
〔耐ソルベントクラック性〕
各ホースから切り出したＪＩＳ１号ダンベルの中心にノッチ傷（２．５ｍｍ）を入れ、これをＦｕｅｌ Ｃ燃料液に浸漬し、４０℃環境下で放置して、ダンベルが破断するまでの時間を測定した。
〈評価〉
○：破断するまでの時間が２分以上のもの
×：破断するまでの時間が２分未満のもの[Solvent crack resistance]
A notch scratch (2.5 mm) was made in the center of a JIS No. 1 dumbbell cut out from each hose, immersed in Fuel C fuel solution, and left in a 40 ° C. environment, and the time until the dumbbell broke was measured. .
<Evaluation>
○: Time until breakage is 2 minutes or more ×: Time until breakage is less than 2 minutes
〔圧縮永久歪性〕
各ゴム組成物を用いて大型試験片（厚さ１２．５±０．５ｍｍ、直径２９．０±０．５ｍｍ）を作製し、温度１００℃、試験時間７２時間、圧縮率２５％で、ＪＩＳ Ｋ ６２６２に準じて、圧縮永久歪性を評価した。
〈評価〉
○：５５％以下のもの
×：５５％を超えるもの[Compression set]
A large test piece (thickness 12.5 ± 0.5 mm, diameter 29.0 ± 0.5 mm) was prepared using each rubber composition, and the temperature was 100 ° C., the test time was 72 hours, and the compression rate was 25%. The compression set was evaluated in accordance with K6262.
<Evaluation>
○: Less than 55% ×: More than 55%
上記表１の結果から、実施例１〜６は、特定の加硫促進剤（Ｂ成分）としてＴＢＺＴおよびＴＯＴ−Ｎのみを所定量含有しているため、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性の全ての性能に優れていた。 From the result of the said Table 1, since Examples 1-6 contain only a predetermined amount of TBZT and TOT-N as a specific vulcanization accelerator (component B), storage stability, solvent crack resistance, compression It was excellent in all the properties of permanent distortion.
これに対して、比較例１〜３は、貯蔵安定性、耐ソルベントクラック性、圧縮永久歪性の何れかの性能が劣っていた。 On the other hand, Comparative Examples 1-3 were inferior in the performance in any one of storage stability, solvent crack resistance, and compression set.
なお、上記実施例においては、本発明における具体的な形態について示したが、上記実施例は単なる例示にすぎず、限定的に解釈されるものではない。また、請求の範囲の均等範囲に属する変更は、全て本発明の範囲内である。 In addition, in the said Example, although it showed about the specific form in this invention, the said Example is only a mere illustration and is not interpreted limitedly. Further, all modifications belonging to the equivalent scope of the claims are within the scope of the present invention.
本発明のゴム組成物は、自動車用燃料輸送ホースや、自動車用燃料シール等の自動車用燃料部材に用いられる。上記自動車用燃料輸送ホースとしては、例えば、燃料（ガソリン、ガソリン蒸気等）と接触する、フィラーネックチューブ、ブリーザーホース、エバポレーションホース、パージホース等があげられる。また、上記自動車用燃料シールとしては、例えば、燃料（ガソリン、ガソリン蒸気等）と接触する、タンクパッキン、ガスケット、Ｏ−リング等があげられる。 The rubber composition of the present invention is used for an automobile fuel member such as an automobile fuel transport hose and an automobile fuel seal. Examples of 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 fuel seal for automobiles include tank packing, gaskets, O-rings, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
Claims (5)
（Ａ）アクリロニトリル−ブタジエンゴム（ＮＢＲ）とポリ塩化ビニル（ＰＶＣ）とのブレンドゴム（ＮＢＲ−ＰＶＣ）、またはＮＢＲ。
（Ｂ）テトラベンジルチウラムジスルフィド（ＴＢＺＴ）、およびテトラビス（２−エチルヘキシル）チウラムジスルフィド（ＴＯＴ−Ｎ）の双方。 A rubber composition used for an automobile fuel member, comprising the following (A) as a main component, containing only the following (B) component as a vulcanization accelerator, and the content of the (B) component is: (a) above rubber composition characterized der Rukoto below 7 parts by weight exceeds 2.5 parts by weight per 100 parts by weight of component.
(A) A blend 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).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012552625A JP5655096B2 (en) | 2011-01-14 | 2011-09-08 | Rubber composition and automobile fuel member using the same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011006045 | 2011-01-14 | ||
| JP2011006045 | 2011-01-14 | ||
| PCT/JP2011/070463 WO2012096031A1 (en) | 2011-01-14 | 2011-09-08 | Rubber composition and automobile fuel system part using same |
| JP2012552625A JP5655096B2 (en) | 2011-01-14 | 2011-09-08 | Rubber composition and automobile fuel member using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2012096031A1 JPWO2012096031A1 (en) | 2014-06-09 |
| JP5655096B2 true JP5655096B2 (en) | 2015-01-14 |
Family
ID=46506948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012552625A Active JP5655096B2 (en) | 2011-01-14 | 2011-09-08 | Rubber composition and automobile fuel member using the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5655096B2 (en) |
| CN (1) | CN103249772B (en) |
| GB (1) | GB2501173B (en) |
| WO (1) | WO2012096031A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010155883A (en) * | 2008-12-26 | 2010-07-15 | Nippon Zeon Co Ltd | Nitrile copolymer rubber composition |
Family Cites Families (6)
| 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 |
| JP4604310B2 (en) * | 2000-05-11 | 2011-01-05 | 東海ゴム工業株式会社 | Manufacturing method of fuel transport hose |
| JP5151129B2 (en) * | 2006-06-16 | 2013-02-27 | Ｎｏｋ株式会社 | Rubber metal laminate |
| JP5096764B2 (en) * | 2007-02-27 | 2012-12-12 | 東海ゴム工業株式会社 | Non-aqueous hose for automobile |
| JP2008239832A (en) * | 2007-03-28 | 2008-10-09 | Jsr Corp | Rubber composition, crosslinked rubber and molded product |
| JP4492647B2 (en) * | 2007-06-21 | 2010-06-30 | 横浜ゴム株式会社 | Adhesive rubber composition for hose |
-
2011
- 2011-09-08 WO PCT/JP2011/070463 patent/WO2012096031A1/en active Application Filing
- 2011-09-08 GB GB1304367.4A patent/GB2501173B/en active Active
- 2011-09-08 JP JP2012552625A patent/JP5655096B2/en active Active
- 2011-09-08 CN CN201180059193.2A patent/CN103249772B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010155883A (en) * | 2008-12-26 | 2010-07-15 | Nippon Zeon Co Ltd | Nitrile copolymer rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201304367D0 (en) | 2013-04-24 |
| CN103249772B (en) | 2014-12-17 |
| GB2501173A8 (en) | 2015-11-11 |
| GB2501173B (en) | 2017-06-14 |
| WO2012096031A1 (en) | 2012-07-19 |
| GB2501173A (en) | 2013-10-16 |
| CN103249772A (en) | 2013-08-14 |
| JPWO2012096031A1 (en) | 2014-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5655096B2 (en) | Rubber composition and automobile fuel member using the same | |
| JP6186251B2 (en) | Rubber composition for inner liner and pneumatic tire | |
| EP3184325B1 (en) | Pneumatic tire for heavy load | |
| WO2012096030A1 (en) | Rubber composition and automobile fuel system part using same | |
| JP2010077233A (en) | Rubber composition for tire and pneumatic tire using the same | |
| JP6332090B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP5991855B2 (en) | Rubber composition | |
| JP2016216549A (en) | Rubber composition and hose using the same | |
| US20010051241A1 (en) | Fuel transporting hose | |
| JP2016098296A (en) | Unvulcanized rubber composition for inner liner and pneumatic tire | |
| JP2013227480A (en) | Rubber composition | |
| JPWO2016143667A1 (en) | Rubber composition and pneumatic tire using the same | |
| JP2010144067A (en) | Rubber composition and pneumatic tire using the same | |
| JP2011116815A (en) | Rubber composition for tire and pneumatic tire obtained using the same | |
| JP6106916B2 (en) | Rubber composition for tire and pneumatic tire using the same | |
| WO2014203695A1 (en) | Rubber composition for vibration-proof rubber | |
| JP2009030037A (en) | Vibration damping rubber composition and vibration damping member | |
| JP6242832B2 (en) | Rubber composition for sidewall and pneumatic tire using the same | |
| JP2006063320A (en) | Resol-type alkylphenol/formaldehyde copolycondensation resin crosslinker | |
| JP2015189794A (en) | Rubber composition and pneumatic tire using the same | |
| JP7382213B2 (en) | Rubber composition for fuel hose and fuel hose obtained using the same | |
| WO2024162168A1 (en) | Fluid hose | |
| JP2013249408A (en) | Rubber composition | |
| JP2016196562A (en) | Rubber composition and pneumatic tire using the same | |
| JP2009091375A (en) | Rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140708 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140804 Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140804 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141104 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141121 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5655096 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |