Classifications

• • 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
• • 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
  • F16L11/06—Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
  • F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
  • F02M37/0011—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor
  • F02M37/0017—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor related to fuel pipes or their connections, e.g. joints or sealings

Definitions

• the present invention relates to a rubber composition used for an automobile fuel member and an automobile fuel member using the same, and more specifically, a filler neck tube, a breather hose, and an evaporator that are in contact with fuel (gasoline, gasoline vapor, etc.).
• a rubber composition used for automobile fuel seals such as fuel tanks, gaskets, O-rings, etc. that contact with fuel (gasoline, gasoline vapor, etc.)
• the present invention relates to an automobile fuel member.
• a rubber composition used for an automobile fuel member such as an automobile fuel transportation hose
• a blend rubber (NBR-PVC) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC), or NBR is used.
• NBR-PVC blend rubber
• PVC polyvinyl chloride
• a low molecular weight thiuram vulcanization accelerator such as tetramethylthiuram disulfide (TMTD) or a sulfenamide vulcanization accelerator is used (see Patent Documents 1 to 4). ).
• JP 2001-72804 A JP 2001-317663 A JP 2008-208267 A JP 2009-1657 A
• low molecular weight thiuram vulcanization accelerators and sulfenamide vulcanization accelerators such as the above-mentioned TMTD have high reaction activity, poor storage stability when rubber is not vulcanized, and dense vulcanization density. Therefore, when it is immersed in fuel oil, it is easy to produce a crack, and there exists a difficulty that it is inferior to solvent crack resistance (performance which suppresses generation
• the content of the low molecular weight thiuram vulcanization accelerator or sulfenamide vulcanization accelerator such as TMTD is reduced, the storage stability and the solvent crack resistance are improved, but the compression set is improved. A new problem of inferiority will occur.
• the present invention has been made in view of such circumstances, and provides a rubber composition excellent in all of the performances of storage stability, solvent crack resistance, and compression set, and an automobile fuel member using the rubber composition. Is the purpose.
• the present invention is a rubber composition used for a fuel member for automobiles, comprising the following (A) as a main component and containing only the following component (B) as a vulcanization accelerator. And let the rubber composition whose content of the said (B) component exceeds 2.5 weight part with respect to 100 weight part of said (A) components be a 1st summary.
• A Blend rubber (NBR-PVC) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC), or NBR.
• NBR-PVC Blend rubber
• NBR acrylonitrile-butadiene rubber
• PVC polyvinyl chloride
• TTZT tetrabenzyl thiuram disulfide
• TOT-N tetrabis (2-ethylhexyl) thiuram disulfide
• the second gist of the present invention is an automobile fuel member using the rubber composition as at least a part of an automobile fuel member.
• TMTD tetramethylthiuram disulfide
• TZT tetrabenzylthiuram disulfide
• TOT-N tetrabis (2-ethylhexyl) thiuram disulfide
• the rubber composition used in the automobile fuel member of the present invention (hereinafter sometimes simply referred to as “rubber composition”) has tetrabenzylthiuram disulfide (TBZT) and tetrabis (TBZT) as vulcanization accelerators.
• TTZT-N 2-ethylhexyl) thiuram disulfide
• component B both of the above TBZT and TOT-N [hereinafter sometimes simply referred to as “TBZT and TOT-N (component B)]” Since the content is set to exceed 2.5 parts by weight with respect to 100 parts by weight of NBR-PVC or NBR (component A), all of storage stability, solvent crack resistance and compression set The effect of excellent performance is obtained.
• the rubber composition of the present invention further contains stearic acid and zinc oxide in addition to the A component and the B component, and the stearic acid content is 0.5 to 100 parts by weight based on 100 parts by weight of the A component.
• the content of zinc oxide is 3 to 10 parts by weight with respect to 100 parts by weight of the component A, stearic acid is used rather than the reaction between the decomposition product of the component B and zinc oxide. Since the reaction between zinc and zinc oxide is prioritized, the balance between storage stability, solvent crack resistance and compression set becomes better.
• An automotive fuel member (automotive fuel transportation hose or automotive fuel seal) using at least a part (or all of the rubber composition) of the present invention is immersed in fuel oil. Since crack generation can be suppressed, it has excellent solvent crack resistance.
• the rubber composition used for the fuel member for automobiles of the present invention includes a blend rubber (NBR-PVC) or NBR (component A) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC), tetrabenzyl thiuram disulfide ( TBZT) and tetrabis (2-ethylhexyl) thiuram disulfide (TOT-N) (B component).
• NBR-PVC blend rubber
• NBR acrylonitrile-butadiene rubber
• PVC polyvinyl chloride
• TBZT tetrabenzyl thiuram disulfide
• TOT-N tetrabis (2-ethylhexyl) thiuram disulfide
• the range is / 20 to 70/30.
• the NBR is preferably one having an acrylonitrile (AN) amount in the range of 25 to 65%, particularly preferably an AN amount in the range of 30 to 60%, from the viewpoint of the balance between the fuel barrier resistance and the low temperature property.
• AN acrylonitrile
• a monomer copolymerizable with the NBR may be blended.
• the PVC preferably has an average degree of polymerization in the range of 700 to 1400, particularly preferably around 800.
• NBR-PVC in which PVC is blended with NBR is more preferable than NBR alone from the viewpoint of ozone resistance.
• component A is the main component
• the phrase “component A is the main component” means that the component A is the main component in the rubber composition of the present invention.
• both TBZT and TOT-N (component B) >>
• thiuram vulcanization accelerators such as tetramethylthiuram disulfide (TMTD) and sulfenamide vulcanization accelerators are used. Contains no agent.
• the total content of both TBZT and TOT-N exceeds 2.5 parts by weight with respect to 100 parts by weight of NBR-PVC or NBR (component A), preferably It is 5 parts by weight or more, most preferably in the range of 5 to 7 parts by weight. That is, if the content of the component B is too small, the compression set is inferior.
• the rubber composition of the present invention includes a processing aid, an antioxidant, a reinforcing agent, a plasticizer, Vulcanizing agents, vulcanization accelerating aids, vulcanization retarders, white fillers, colorants and the like may be appropriately blended as necessary.
• processing aids include stearic acid, fatty acid esters, fatty acid amides, hydrocarbon resins and the like, and are used alone or in combination of two or more.
• stearic acid is preferable from the viewpoint of the balance between storage stability, solvent crack resistance, and compression set.
• the content of the processing aid is usually set in the range of 0.1 to 10 parts by weight, preferably 0.5 to 1.5 parts per 100 parts by weight of the NBR-PVC or NBR (component A).
• the range is parts by weight.
• Anti-aging agent examples include phenylenediamine-based anti-aging agents, phenol-based anti-aging agents, diphenylamine-based anti-aging agents, quinoline-based anti-aging agents, waxes and the like, and are used alone or in combination of two or more. .
• the content of the anti-aging agent is usually set in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the component A.
• ⁇ Reinforcing agent examples include carbon black, silica and the like, and they are used alone or in combination of two or more.
• Examples of the carbon black include grades such as SAF class, ISAF class, HAF class, MAF class, FEF class, GPF class, SRF class, FT class, and MT class. These may be used alone or in combination of two or more.
• the content of the reinforcing agent is usually set in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the component A.
• plasticizer examples include phthalic acid plasticizers such as di-2-ethylhexyl phthalate (DOP) and di-n-butyl phthalate (DBP), and adipic acid such as dibutyl carbitol adipate and dioctyl adipate (DOA).
• Plasticizers, sebacic acid plasticizers such as dioctyl sebacate (DOS), dibutyl sebacate (DBS), phosphate plasticizers such as tricresyl phosphate (TCP), and polyether plasticizers. . These may be used alone or in combination of two or more.
• the content of the plasticizer is usually set in the range of 5 to 100 parts by weight with respect to 100 parts by weight of the component A.
• vulcanizing agent examples include sulfur compounds such as sulfur, morpholine and disulfide, organic peroxides, and the like, and they are used alone or in combination of two or more.
• the content of the vulcanizing agent is usually set in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the component A.
• vulcanization acceleration aid examples include zinc oxide, activated zinc white, magnesium oxide, and the like, and they are used alone or in combination of two or more. Among these, zinc oxide is preferable from the viewpoint of balance between storage stability, solvent crack resistance, and compression set.
• the content of the vulcanization accelerator aid is usually set in the range of 0.5 to 10 parts by weight, preferably in the range of 3 to 10 parts by weight, with respect to 100 parts by weight of the component A.
• vulcanization retarder examples include N- (cyclohexylthio) phthalimide.
• the content of the vulcanization retarder is usually set in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the component A.
• filler examples include calcium carbonate, magnesium carbonate, clay, talc, mica and the like, and they are used alone or in combination of two or more.
• the content of the filler is usually set in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the component A.
• the rubber composition of the present invention contains a predetermined amount of both TBZT and TOT-N (component B) in the NBR-PVC or NBR (component A), and, if necessary, carbon black, an antioxidant, etc. And kneading them using a kneader such as a kneader, a Banbury mixer, or a roll.
• a kneader such as a kneader, a Banbury mixer, or a roll.
• the rubber composition of the present invention is used for at least a part (or all) of an automobile fuel member such as an automobile fuel transport hose or an automobile fuel seal.
• an automobile fuel member such as an automobile fuel transport hose or an automobile fuel seal.
• the fuel transportation hose for automobiles include a filler neck tube, a breather hose, an evaporation hose, a purge hose, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
• Examples of the automobile fuel seal include tank packing, gaskets, O-rings, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
• the automobile fuel transport hose of the present invention (hereinafter, abbreviated as “fuel transport hose” as appropriate) can be produced, for example, as follows. That is, the rubber composition prepared as described above is extruded using an extruder, and this is steam vulcanized (for example, 155 ° C. ⁇ 20 minutes) to obtain a fuel transport hose having a single layer structure. be able to. Note that a mandrel may be used as necessary.
• a glycol-based mold release agent for example, polyethylene glycol (PEG), polypropylene glycol (PPG) and a mixture thereof
• silicone emulsion-based mold release is provided on either or both of the inner peripheral surface of the hose and the outer peripheral surface of the mandrel.
• a release agent such as an agent may be applied.
• the fuel transport hose of the present invention is not limited to a single layer structure, and may have a multilayer structure in which at least one layer is formed on the outer periphery thereof, and may be reinforced to a part of the multilayer structure hose.
• a layer may be formed.
• the inner diameter of the hose is preferably in the range of 2 to 100 mm, particularly preferably in the range of 5 to 50 mm, and the thickness of the hose is preferably in the range of 0.5 to 20 mm, particularly preferably 1 to 10 mm. Range.
• Nipol DN508SCR (AN amount: 38.0%) manufactured by Nippon Zeon
• TZT Tetrabenzylthiuram disulfide
• component B Accelerator TBZT, manufactured by Kawaguchi Chemical Co., Ltd.
• TOT-N Tetrabis (2-ethylhexyl) thiuram disulfide (component B)] Nouchira TOT-N, manufactured by Ouchi Shinsei Chemical Co., Ltd.
• TMTD Tetramethylthiuram disulfide
• Stearic acid manufactured by Kao Corporation, LUNAC S-70V
• Anti-aging agent (i) ANTAGE 3C, manufactured by Kawaguchi Chemical Co., Ltd.
• Anti-aging agent (ii)) ANTAGE RD manufactured by Kawaguchi Chemical Co., Ltd.
• Examples 1 to 6, Comparative Examples 1 to 3 The components shown in Table 1 below were blended in the proportions shown in the same table, and kneaded using a 3 L kneader to prepare a rubber composition. Next, the rubber composition was extruded with an extruder and steam vulcanized (155 ° C. ⁇ 20 minutes) to produce a fuel transport hose having a single layer structure (inner diameter 30 mm, thickness 3 mm).
• Examples 1 to 6 contain only a predetermined amount of TBZT and TOT-N as specific vulcanization accelerators (component B), so that storage stability, solvent crack resistance, compression It was excellent in all the properties of permanent distortion.
• Comparative Examples 1 to 3 were inferior in any of storage stability, solvent crack resistance, and compression set properties.
• the rubber composition of the present invention is used in automobile fuel members such as automobile fuel transport hoses and automobile fuel seals.
• automobile fuel members such as automobile fuel transport hoses and automobile fuel seals.
• the fuel transportation hose for automobiles include a filler neck tube, a breather hose, an evaporation hose, a purge hose, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).
• automobile fuel seal include tank packing, gaskets, O-rings, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).

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• 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)

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• 2011
  • 2011-09-08 GB GB1304367.4A patent/GB2501173B/en active Active
  • 2011-09-08 JP JP2012552625A patent/JP5655096B2/ja active Active
  • 2011-09-08 CN CN201180059193.2A patent/CN103249772B/zh active Active
  • 2011-09-08 WO PCT/JP2011/070463 patent/WO2012096031A1/ja active Application Filing

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