WO2020261867A1 - オイルホース - Google Patents

オイルホース Download PDF

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Publication number
WO2020261867A1
WO2020261867A1 PCT/JP2020/021098 JP2020021098W WO2020261867A1 WO 2020261867 A1 WO2020261867 A1 WO 2020261867A1 JP 2020021098 W JP2020021098 W JP 2020021098W WO 2020261867 A1 WO2020261867 A1 WO 2020261867A1
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Prior art keywords
weight
hose
oil
parts
innermost layer
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PCT/JP2020/021098
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English (en)
French (fr)
Japanese (ja)
Inventor
神戸　忍
絢深 野末
皓一朗 川井
高行 若野
Original Assignee
住友理工株式会社
住友理工ホーステックス株式会社
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Application filed by 住友理工株式会社, 住友理工ホーステックス株式会社 filed Critical 住友理工株式会社
Priority to CN202080042675.6A priority Critical patent/CN113950502B/zh
Priority to JP2021520430A priority patent/JP6975363B2/ja
Publication of WO2020261867A1 publication Critical patent/WO2020261867A1/ja

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    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/02—Layer formed of wires, e.g. mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • 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
    • 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
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • 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
    • F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
    • 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
    • F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
    • F16L57/02—Protection of pipes or objects of similar shape against external or internal damage or wear against cracking or buckling
    • 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
    • F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
    • F16L57/04—Protection of pipes or objects of similar shape against external or internal damage or wear against fire or other external sources of extreme heat
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes

Definitions

  • the present invention relates to an oil hose used for various oil transport hoses such as a high-pressure hydraulic hose for construction machinery (construction machinery) and mining machinery, and an engine oil hose for automobiles.
  • the material of the innermost layer of the hose is, for example, acrylonitrile butadiene rubber having excellent oil resistance and heat resistance. Etc. are used (see Patent Documents 1 to 3).
  • ZnDTP zinc dialkyldithiophosphate
  • ZnDTP is widely known as a multifunctional additive for industrial oils having an antioxidant ability, a corrosion preventing ability, a load bearing performance, an abrasion preventing ability and the like.
  • the oil hose using the innermost layer material using acrylonitrile butadiene rubber as a polymer has a problem that the resistance to the oil to which ZnDTP is added tends to be insufficient.
  • ZnDTP contained in the oil was oxidized and decomposed by itself instead of the oil to exhibit antioxidant ability, etc., but due to the above decomposition , Generates acidic substances (sulfuric acid, zinc sulfate).
  • the innermost layer is required to have cold resistance and the like in addition to suppressing rubber deterioration due to permeation of the oxidatively deteriorated oil. Therefore, an oil hose that improves these problems and exhibits high resistance to oil to which ZnDTP is added is required.
  • the present invention has been made in view of such circumstances, and is an oil which is excellent in characteristics required for an oil hose such as oil resistance, cold resistance, and heat resistance, and also exhibits high resistance to oil to which ZnDTP is added.
  • an oil hose such as oil resistance, cold resistance, and heat resistance
  • high resistance to oil to which ZnDTP is added Provide a hose.
  • the present inventors have conducted extensive research to solve the above problems.
  • the present inventors added zinc oxide, a specific thiuram-based vulcanization accelerator, an ether ester-based plasticizer, and sulfur to the polymer acrylonitrile butadiene rubber in the innermost layer material of the oil hose.
  • the ratio of the zinc oxide and the specific thiuram-based vulcanization accelerator was set in a specific range, and the acrylonitrile butadiene rubber was used in a specific range in the amount of the acrylonitrile, oil resistance was obtained.
  • the ether ester-based plasticizer in the innermost layer material is decomposed by the acidic substance (the ester bond portion of the plasticizer is decomposed) and decomposed into an alcohol component and a carboxylic acid component having an ether bond
  • the specific carboxylic acid component is low in molecular weight and highly polar, it easily bleeds on the inner peripheral surface of the hose.
  • the decomposition salt of zinc oxide and a specific thiuram-based vulcanization accelerator (zinc salt of thiuram) is also bleeded by the specific carboxylic acid component, and the inner circumference of the hose. It becomes easier to move (bloom) to the vicinity of the surface.
  • the decomposed salt functions well as an acid receiving component of the acidic substance near the inner peripheral surface of the hose, and erosion of the innermost layer of the hose by the acidic substance can be effectively suppressed. Guessed.
  • the gist of the present invention is the following [1] to [8].
  • (A) Acrylonitrile butadiene rubber having an acrylonitrile content of 26 to 38% by weight.
  • B Zinc oxide.
  • C At least one thiuram-based vulcanization accelerator selected from the group consisting of tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and dipentamethylene thiuram tetrasulfide.
  • D Ether ester plasticizer.
  • [2] The oil hose according to [1], wherein the ether ester plasticizer (D) is an ether ester plasticizer having a molecular weight of 350 to 1000.
  • the oil hose is composed of a plurality of constituent layers, and has a reinforcing layer made of plated wire and a rubber layer in contact with the reinforcing layer on the outer periphery of the innermost layer thereof, [1] to The oil hose according to any one of [4].
  • (X) The ratio of zinc atoms to carbon atoms (Zn / C) as measured by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the oil hose of the present invention is excellent in the characteristics required for the oil hose, such as oil resistance, cold resistance, and heat resistance, and can exhibit high resistance to oil to which ZnDTP is added.
  • the oil hose of the present invention is an oil hose composed of at least one constituent layer, the innermost layer thereof containing the following components (A) to (E), and the component (A) 100.
  • the component (B) is 4 to 15 parts by weight
  • the component (C) is 0.5 to 3 parts by weight
  • the component (D) is 1 to 15 parts by weight
  • the component (E) is 0.25 to parts by weight.
  • (A) Acrylonitrile butadiene rubber (NBR) having an acrylonitrile content of 26 to 38% by weight.
  • NBR Acrylonitrile butadiene rubber
  • the oil hose of the present invention is composed of at least one constituent layer, and the innermost layer thereof is composed of the rubber composition shown above. Therefore, when the oil hose of the present invention has a single-layer structure, its layer is composed of the rubber composition shown above, and when it has a multi-layer structure, its innermost layer is composed of the rubber composition shown above.
  • the constituent materials of the rubber composition will be described in detail.
  • NBR (A) As the NBR (A), one having an acrylonitrile amount (AN amount) in the range of 26 to 38% by weight is used, and one having an AN amount in the range of 27 to 33% by weight is preferably used. That is, if the AN amount of NBR is less than the above range, the oxidatively deteriorated oil tends to permeate into the innermost layer and the rubber tends to be deteriorated. On the contrary, the AN amount of NBR exceeds the above range. This is because the cold resistance and the like tend to decrease as the rubber of the innermost layer deteriorates.
  • 80% by weight or more of the polymer component of the rubber composition is preferably NBR (A) having an AN amount in the above range, and more preferably 90% by weight or more of the polymer component.
  • the amount of AN is NBR (A) in the above range, and more preferably, the above-mentioned polymer component is composed of only NBR (A) having an amount of AN in the above range.
  • zinc oxide (B) examples include zinc oxide type 1, zinc oxide type 2, zinc oxide type 3, fine zinc oxide and the like. These may be used alone or in combination of two or more.
  • the content of zinc oxide (B) in the rubber composition is in the range of 4 to 15 parts by weight, preferably in the range of 7 to 13 parts by weight, based on 100 parts by weight of NBR (A).
  • Thiuram-based vulcanization accelerator (C) thiuram-based vulcanization accelerator
  • thiuram-based vulcanization accelerator (C) tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and dipentamethylene thiuram tetrasulfide are used alone or in combination of two or more. That is, in these specific vulcanization accelerators, zinc oxide and the decomposition salt which is a reaction product are more soluble in oil than other vulcanization accelerators and other vulcanization accelerators.
  • the content of the thiuram-based vulcanization accelerator (C) in the rubber composition is in the range of 0.5 to 3 parts by weight, preferably 1 to 2 parts by weight, based on 100 parts by weight of NBR (A). , More preferably in the range of 1.3 to 1.7 parts by weight.
  • the "ether ester-based plasticizer” refers to a plasticizer having both an ether bond and an ester bond in one molecule. Since it is such a plasticizer, the zinc oxide in the innermost layer of the hose and the decomposition salt of a specific thiuram-based vulcanization accelerator (zinc salt of thiuram) are promoted to bloom to the inner peripheral surface of the hose, and the ZnDTP decomposition product Erosion of the innermost layer of the hose by (acidic substance) can be effectively suppressed.
  • the molecular weight of the ether ester plasticizer (D) is preferably 350 to 1000, and more preferably the molecular weight is in the range of 400 to 600. That is, when such a low molecular weight plasticizer is used, zinc oxide in the innermost layer of the hose is specified by the acidic substance which is a decomposition product of ZnDTP and the carboxylic acid component having an ether bond generated from the ether ester plasticizer. Blooming of the decomposition salt of the thiuram-based plasticizer (zinc oxide of thiuram) to the inner peripheral surface of the hose is promoted, and erosion of the innermost layer of the hose by ZnDTP decomposition products (acidic substances) can be suppressed more effectively. ..
  • ether ester-based plasticizer (D) examples include adipic acid ether ester-based plasticizers such as bis (2- (2-butoxyethoxy) ethyl] adipate, and various polyether ester-based plasticizers. Plasticizers may be used alone or in combination of two or more.
  • ether ester-based plasticizer (D) commercially available products include ADEKA Sizer RS-107, ADEKA Sizer RS-700, ADEKA Sizer RS-735, ADEKA Sizer RS-830, and ADEKA Sizer RS-966.
  • ADEKA Sizer RS-1000 aboveve, manufactured by ADEKA
  • thiocol TP-95, thiocol TP-759 aboveve, manufactured by HALLSTAR
  • the content of the ether ester plasticizer (D) in the rubber composition is in the range of 1 to 15 parts by weight, preferably in the range of 3 to 15 parts by weight, based on 100 parts by weight of NBR (A). More preferably, it is in the range of 7 to 10 parts by weight. That is, if the content of the ether ester-based plasticizer (D) is too small, zinc oxide in the innermost layer of the hose and a decomposition salt of a specific thiuram-based sulfide accelerator (zinc salt of thiuram) are transferred to the inner peripheral surface of the hose.
  • a decomposition salt of a specific thiuram-based sulfide accelerator zinc salt of thiuram
  • sulfur (E) for example, not only sulfur such as powdered sulfur, precipitated sulfur, and insoluble sulfur, but also a sulfur-containing compound such as alkylphenol disulfide may be used. These may be used alone or in combination of two or more.
  • the content of sulfur (E) is in the range of 0.25 to 2 parts by weight, preferably in the range of 0.3 to 1.5 parts by weight, and more preferably in the range of 0.3 to 1.5 parts by weight with respect to 100 parts by weight of NBR (A). It is in the range of 0.4 to 0.7 parts by weight. That is, if the content of the sulfur (E) is too small, the cross-linking reactivity tends to deteriorate, and conversely, if the content of the sulfur (E) is too large, the rubber physical properties (breaking strength, breaking elongation). This is because there is a tendency for the value to decrease.
  • the rubber composition which is the innermost material of the oil hose of the present invention, contains carbon black, silica, a silane coupling agent, a co-crosslinking agent, a vulcanization accelerator, and processing.
  • Auxiliary agents stearic acid, etc.
  • anti-aging agents flame retardants, anti-scorch agents, etc. may be added as needed.
  • the content of the carbon black is preferably in the range of 20 to 70 parts by weight, and more preferably in the range of 30 to 50 parts by weight with respect to 100 parts by weight of NBR (A). ..
  • the silica content is preferably in the range of 20 to 60 parts by weight, more preferably 30 to 60 parts by weight, based on 100 parts by weight of NBR (A), from the viewpoint of heat aging and adsorption of acid components. It is in the range of 50 parts by weight.
  • a silane coupling agent together with the above silica from the viewpoint of suppressing the penetration of oxidatively deteriorated oil into the innermost layer of the hose and more effectively suppressing the erosion of the innermost layer of the hose.
  • the oil hose of the present invention may have a single-layer structure or a multi-layer structure, but from the viewpoint of reinforcing property and the like, it is preferable to have a multi-layer structure.
  • the oil hose of the present invention is composed of a plurality of constituent layers in this way, and a reinforcing layer made of a plated wire (plated wire) and a rubber layer in contact with the reinforcing layer are formed on the outer periphery of the innermost layer thereof. It is preferable to provide (see FIG. 1).
  • the reinforcing layer is a layer formed by braiding plated wires into a blade shape, a spiral shape, or the like in order to reinforce the strength of the entire hose.
  • Examples of the plating treatment in the plated wire include copper plating, zinc plating, brass (copper-zinc alloy) plating, nickel plating, tin plating, cobalt plating and the like, and brass plating is preferable.
  • the diameter of the plated wire is usually in the range of 0.1 to 1.2 mm, preferably in the range of 0.2 to 0.8 mm.
  • Rubber layer other than the innermost layer rubber having excellent weather resistance is preferable as the forming material thereof.
  • chloroprene rubber (CR) chloroprene rubber
  • SBR styrene-butadiene rubber
  • EPDM ethylene-propylene-diene rubber
  • SBR and EPDM blended rubber SBR and EPDM blended rubber
  • NBR and EPDM blended rubber NBR and vinyl chloride (PVC) blended rubber
  • acrylic rubber (ACM) ethylene acrylate rubber (AEM), chlorinated polyethylene (CM), chlorosulfonated
  • CSM polyethylene
  • rubber such as CR, reinforcing materials (carbon black, etc.), white fillers, plasticizers, stearic acid, zinc oxide, acid receiving agents (highly activated magnesium, hydrotalcite, etc.), anti-aging Agents, vulcanizing agents, vulcanizing agent accelerators, processing aids and the like may be appropriately added as necessary.
  • the oil hose of the present invention has a layer structure as shown in FIG. 1, for example, it can be produced as follows. That is, first, as the material for the innermost layer 1, each component material of the components (A) to (E) is prepared, and if necessary, other component materials are also prepared, and these are used in a roll, kneader, vanbury mixer, etc. A rubber composition for forming the innermost layer 1 is prepared by kneading using a kneader. Then, using an extrusion molding machine, the rubber composition for forming the innermost layer 1 is extruded onto a mandrel to form the innermost layer 1.
  • the reinforcing layer 2 is formed by braiding the plated wire in a spiral shape on the outer peripheral surface of the innermost layer 1 using a braiding machine.
  • the rubber composition for forming the outer layer 3 is extruded onto the outer peripheral surface of the reinforcing layer 2 to form the outer layer 3.
  • the inner diameter of the hose is usually in the range of 3 to 100 mm, preferably 6 to 65 mm, and the outer diameter of the hose is usually in the range of 7 to 150 mm, preferably 10 to 90 mm. is there.
  • the thickness of the innermost layer 1 is usually in the range of 0.6 to 4 mm, preferably in the range of 1 to 3 mm.
  • the thickness of the outer layer 3 is usually in the range of 0.2 to 4 mm, preferably in the range of 0.6 to 3 mm.
  • the oil hose of the present invention is not limited to the three-layer structure as shown in FIG. 1, but has a single-layer structure consisting of only the innermost layer 1, or a reinforcing layer 2 or a reinforcing layer 2 or the outer periphery of the innermost layer 1. It may have a two-layer structure in which only the outer layer 3 is laminated. Further, the structure may be such that two or more layers of the reinforcing layer 2 and the outer layer 3 are alternately laminated. Further, in addition to a wire layer such as the reinforcing layer 2 and a rubber layer different from the innermost layer 1 such as the outer layer 3, a resin layer, a reinforcing thread layer, or the like is provided as necessary on the outer periphery of the innermost layer 1. May be formed in.
  • the oil hose of the present invention obtained as described above has a depth of less than 100 ⁇ m from the inner peripheral surface of the hose when oil at 100 ° C. containing 0.9% by weight of ZnDTP is circulated in the hose for 500 hours. It is desirable that the value of the following (X) in the range of the innermost layer of the hose is higher than the value of the following (X) in the range of the innermost layer having a depth of 100 to 500 ⁇ m from the inner peripheral surface of the hose.
  • the value of the following (X) in the range of the innermost layer from the inner peripheral surface of the hose to a depth of less than 100 ⁇ m is 0.01 to 0.015 (more preferably 0.011 to 0.015, More preferably, it is 0.013 to 0.015), and the value of the following (X) in the range of the innermost layer having a depth of 100 to 500 ⁇ m from the inner peripheral surface of the hose is less than 0.01 (more preferably less than 0.009). , More preferably less than 0.007).
  • (X) The ratio of zinc atoms to carbon atoms (Zn / C) as measured by X-ray photoelectron spectroscopy (XPS).
  • the ratio of zinc atoms to carbon atoms (Zn / C) by XPS is measured, for example, under the following conditions. ⁇ XPS measurement conditions ⁇ Measuring device: PHI5000 VersaProbe II (manufactured by ULVAC-PHI) Irradiation X-ray: Al K ⁇ Monochromatic X-ray Output: 25W, 15kV Photoelectron extraction angle: 45 degrees Charge neutralization: Ar ion beam and electron beam Analysis area: Spot analysis (100 ⁇ m ⁇ )
  • the oil hose of the present invention is particularly preferably used as a hose for circulating oil containing ZnDTP, but can also be used as a hose for circulating oil not containing ZnDTP. Further, the oil hose of the present invention can be used for all hoses that require pressure resistance, for example, for construction machinery, mining machines, industrial vehicles (forklifts, automatic guided vehicles, etc.), engine oil hoses for automobiles, and the like. Can be used. Then, it is particularly suitably used as a high-pressure hydraulic hose for construction machinery and mining machinery.
  • Nipole DN302 manufactured by Zeon Corporation, AN amount: 27.5% by weight
  • Nipole DN202 manufactured by Zeon Corporation, AN amount: 31.0% by weight
  • Nipole DN401 manufactured by Zeon Corporation, AN amount: 18.0% by weight
  • Nipole DN4050 manufactured by Zeon Corporation, AN amount: 40.0% by weight
  • Examples 1 to 17, Comparative Examples 1 to 12 Each of the above materials was kneaded at the ratios shown in Tables 1 to 3 below to prepare a rubber composition.
  • materials other than the vulcanizing agent and the vulcanization accelerator are kneaded using a Banbury mixer, then the vulcanizing agent and the vulcanization accelerator are mixed, and the mixture is kneaded using an open roll. I went by.
  • a mandrel was inserted into the extruded rubber composition and steam vulcanized at 150 ° C. for 60 minutes to prepare an oil hose (inner diameter 12 mm) having a thickness of 5 mm.
  • test piece cut out from each oil hose is immersed in the test solution "CF-30" (diesel engine oil manufactured by JX Nikko Nisseki Energy Co., Ltd.) in accordance with JIS K 6258: 2010 at 135 ° C for 480 hours.
  • a test was conducted in which the mixture was heated and acid-deteriorated by the ZnDTP decomposition product in the test solution. Then, the elongation (residual elongation (%)) of the test piece was measured according to JIS K 6251: 2010.
  • the rate of decrease in elongation ( ⁇ EB (%)) after the acid deterioration test was calculated from the difference from the previously measured elongation of the physical properties under normal conditions (initial elongation). Then, the oil resistance was evaluated according to the following criteria. ⁇ : Residual growth of 80% or more. X: Residual growth is less than 80%.
  • ⁇ Cold resistance> The low temperature embrittlement temperature (° C.) was measured for the test piece cut out from each oil hose in accordance with the low temperature impact embrittlement test specified in JIS K 6261: 2006. Then, the cold resistance was evaluated according to the following criteria. ⁇ : ⁇ 30 ° C. or lower. ⁇ : Higher than -30 ° C and lower than -20 ° C. X: -20 ° C or higher.
  • Comparative Example 1 the proportion of the thiuram-based vulcanization accelerator was too small, and the zinc salt of thiuram sufficient to suppress the acid deterioration of the rubber due to the ZnDTP decomposition product bloomed. As a result, the oil resistance was inferior.
  • Comparative Example 2 the ratio of the thiuram-based vulcanization accelerator was too large, and the elongation under normal conditions was reduced, so that the residual elongation after immersion in CF-30 was also reduced, which adversely affected the physical properties and oil resistance under normal conditions. Has reached.
  • Comparative Example 3 the proportion of zinc oxide was too small, and the zinc salt of thiuram sufficient to suppress the acid deterioration of the rubber due to the ZnDTP decomposition product did not bloom, resulting in poor oil resistance.
  • Comparative Example 4 the proportion of zinc oxide was too large and the rubber itself became brittle, resulting in inferior oil resistance.
  • Comparative Example 5 the proportion of the ether ester-based plasticizer was too large, and the oil easily penetrated into the rubber, resulting in inferior oil resistance.
  • Comparative Example 12 since the blending amount of the ether ester plasticizer was not sufficient, the bloom of the zinc salt of thiuram sufficient to suppress the acid deterioration of the rubber due to the ZnDTP decomposition product was not promoted, resulting in poor oil resistance.
  • Comparative Example 9 the AN amount of NBR was too high, resulting in inferior cold resistance and the like.
  • Comparative Examples 10 and 11 a thiuram-based vulcanization accelerator different from that used in the present invention was used, and the desired oil resistance (acid deterioration resistance) required for the present invention could not be obtained. It was.
  • Example 2 the Zn / C value is in the range of 0.01 to 0.015 up to a depth of less than 100 ⁇ m, and less than 0.01 at a depth of 100 ⁇ m to 500 ⁇ m. is there.
  • Example 6 the Zn / C value is in the range of 0.01 to 0.015 up to a depth of less than 100 ⁇ m, but is 0.01 or more at a depth of 100 ⁇ m to 500 ⁇ m.
  • Table 1 the oil hoses of Examples 2 and 6 have very close material compositions to each other, but Example 2 is superior in evaluation of oil resistance and the like. This result is considered to be due to the difference in Zn / C values shown in Table 4 above.
  • the oil hose of the present invention is a hose used for various oil transport hoses, and can be used for all hoses that require pressure resistance.
  • it can be used for construction machinery, mining machinery, industrial vehicles (forklifts, automatic guided vehicles, etc.), engine oil hoses for automobiles, etc., and is particularly preferably used as a high-pressure hydraulic hose for construction machinery and mining machinery.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023120213A1 (ja) * 2021-12-24 2023-06-29 住友理工株式会社 産業用ホース

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07197061A (ja) * 1993-12-28 1995-08-01 Tonen Corp 潤滑油組成物
JP2009203369A (ja) * 2008-02-28 2009-09-10 Jsr Corp 高硬度ゴム製品用組成物及び高硬度ゴム製品
JP2014190373A (ja) * 2013-03-26 2014-10-06 Tokai Rubber Ind Ltd ホース
JP2015101693A (ja) * 2013-11-27 2015-06-04 三菱電線工業株式会社 ゴム組成物およびシール部材
JP2016030784A (ja) * 2014-07-28 2016-03-07 横浜ゴム株式会社 ゴム組成物、ゴム組成物金属積層体、加硫ゴム製品及びゴム組成物金属積層体の製造方法
JP2016070347A (ja) * 2014-09-29 2016-05-09 豊田合成株式会社 自動車用エアーホース
WO2017022598A1 (ja) * 2015-08-05 2017-02-09 日本ゼオン株式会社 ニトリル基含有高飽和共重合体ゴム、架橋性ゴム組成物、およびゴム架橋物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4172151B2 (ja) * 1998-11-04 2008-10-29 日本ゼオン株式会社 燃料ホース用ポリブレンド組成物、架橋物および燃料ホース
JP4461932B2 (ja) * 2004-07-08 2010-05-12 Ｊｓｒ株式会社 耐燃料油性ゴム組成物及び加硫ゴム
US20150175774A1 (en) * 2012-08-09 2015-06-25 Nok Corporation Nbr composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07197061A (ja) * 1993-12-28 1995-08-01 Tonen Corp 潤滑油組成物
JP2009203369A (ja) * 2008-02-28 2009-09-10 Jsr Corp 高硬度ゴム製品用組成物及び高硬度ゴム製品
JP2014190373A (ja) * 2013-03-26 2014-10-06 Tokai Rubber Ind Ltd ホース
JP2015101693A (ja) * 2013-11-27 2015-06-04 三菱電線工業株式会社 ゴム組成物およびシール部材
JP2016030784A (ja) * 2014-07-28 2016-03-07 横浜ゴム株式会社 ゴム組成物、ゴム組成物金属積層体、加硫ゴム製品及びゴム組成物金属積層体の製造方法
JP2016070347A (ja) * 2014-09-29 2016-05-09 豊田合成株式会社 自動車用エアーホース
WO2017022598A1 (ja) * 2015-08-05 2017-02-09 日本ゼオン株式会社 ニトリル基含有高飽和共重合体ゴム、架橋性ゴム組成物、およびゴム架橋物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023120213A1 (ja) * 2021-12-24 2023-06-29 住友理工株式会社 産業用ホース

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