WO2012096031A1 - Rubber composition and automobile fuel system part using same - Google Patents

Rubber composition and automobile fuel system part using same Download PDF

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Publication number
WO2012096031A1
WO2012096031A1 PCT/JP2011/070463 JP2011070463W WO2012096031A1 WO 2012096031 A1 WO2012096031 A1 WO 2012096031A1 JP 2011070463 W JP2011070463 W JP 2011070463W WO 2012096031 A1 WO2012096031 A1 WO 2012096031A1
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Prior art keywords
component
weight
parts
rubber composition
nbr
Prior art date
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PCT/JP2011/070463
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French (fr)
Japanese (ja)
Inventor
野田　将司
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東海ゴム工業株式会社
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Application filed by 東海ゴム工業株式会社 filed Critical 東海ゴム工業株式会社
Priority to GB1304367.4A priority Critical patent/GB2501173B/en
Priority to CN201180059193.2A priority patent/CN103249772B/en
Priority to JP2012552625A priority patent/JP5655096B2/en
Publication of WO2012096031A1 publication Critical patent/WO2012096031A1/en

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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)

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

ゴム組成物およびそれを用いた自動車用燃料部材Rubber composition and automobile fuel member using the same
　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.). 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.
　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). ).
特開２００１－７２８０４号公報JP 2001-72804 A 特開２００１－３１７６６３号公報JP 2001-317663 A 特開２００８－２０８２６７号公報JP 2008-208267 A 特開２００９－１６５７号公報JP 2009-1657 A
　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重量部を超えているゴム組成物を第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 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.
(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。 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.
　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重量部を超えるように設定すると、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 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. When the contents of TBZT and TOT-N are set to exceed 2.5 parts by weight with respect to 100 parts by weight of NBR-PVC or NBR, the performance of both storage stability and solvent crack resistance is reduced. Thus, 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.
　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重量部を超えるよう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 of the above TBZT and TOT-N (component B) [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.
　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 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.
　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重量部を超えるように設定されている。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), tetrabenzyl thiuram 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 100 parts by weight of NBR-PVC or NBR (component A). In contrast, it is set to exceed 2.5 parts by weight. 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 (component A) >>
In the above 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. The range is / 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 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.
　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 A component in the rubber composition of the present invention, NBR-PVC in which PVC is blended with NBR is more preferable than 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 is the main component” means that the component A is the 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 (component B) >>
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重量部を超えており、好ましくは５重量部以上、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) 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.
　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 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.
《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 the 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 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.
　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。 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.
《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。 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.
《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。 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.
　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。 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.
　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 automobile fuel seal 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 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. 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-benzothiazolesulfenamide (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 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).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　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。 Each characteristic was evaluated according to the following criteria using the fuel transport hoses of the examples and comparative examples thus obtained. 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 placed 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 to break is 2 minutes or more ×: Time to break 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 results in Table 1 above, 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.
　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 to 3 were inferior in any of storage stability, solvent crack resistance, and compression set properties.
　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, although the specific form in this invention was shown in the said Example, 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 in automobile fuel members such as automobile fuel transport hoses and automobile fuel seals. 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 automobile fuel seal include tank packing, gaskets, O-rings, etc. that come into contact with fuel (gasoline, gasoline vapor, etc.).

Claims (5)

  1. 　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重量部を超えていることを特徴とするゴム組成物。
    （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: The rubber composition characterized by exceeding 2.5 parts by weight with respect to 100 parts by weight of the 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).
  2. 　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の範囲である請求項１記載のゴム組成物。 The rubber composition according to claim 1, wherein the weight mixing ratio of TBZT (B1) to TOT-N (B2) in the component (B) is in the range of B1 / B2 = 99/1 to 50/50.
  3. 　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重量部である請求項１または２記載のゴム組成物。 It contains stearic acid and zinc oxide, the stearic acid content is 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the component (A), and the zinc oxide content is 100 parts of the component (A). The rubber composition according to claim 1 or 2, which is 3 to 10 parts by weight with respect to parts by weight.
  4. 　請求項１～３のいずれか一項に記載のゴム組成物を、自動車用燃料部材の少なくとも一部に用いてなることを特徴とする自動車用燃料部材。 An automotive fuel member comprising the rubber composition according to any one of claims 1 to 3 as at least a part of an automotive fuel member.
  5. 　自動車用燃料部材が、自動車用燃料輸送ホースまたは自動車用燃料シールである請求項４記載の自動車用燃料部材。 The automobile fuel member according to claim 4, wherein the automobile fuel member is an automobile fuel transport hose or an automobile fuel seal.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015123676A (en) * 2013-12-26 2015-07-06 ダイキン工業株式会社 Laminate
JP2018052054A (en) * 2016-09-30 2018-04-05 住友理工株式会社 Hose manufacturing method
JP2019199549A (en) * 2018-05-16 2019-11-21 Nok株式会社 Rubber composition and seal material

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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)

* Cited by examiner, † Cited by third party
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015123676A (en) * 2013-12-26 2015-07-06 ダイキン工業株式会社 Laminate
JP2018052054A (en) * 2016-09-30 2018-04-05 住友理工株式会社 Hose manufacturing method
JP2019199549A (en) * 2018-05-16 2019-11-21 Nok株式会社 Rubber composition and seal material

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