WO2020261867A1 - Oil hose - Google Patents

Oil hose 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
Prior art date
Application number
PCT/JP2020/021098
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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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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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 JP2021520430A priority Critical patent/JP6975363B2/en
Priority to CN202080042675.6A priority patent/CN113950502B/en
Publication of WO2020261867A1 publication Critical patent/WO2020261867A1/en

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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 general shape other than plane
    • 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.

Abstract

This oil hose is provided with an innermost layer 1 comprising a rubber composition containing components (A)-(E), wherein contained amounts of components (B), (C), (D), and (E) with respect to 100 parts by weight of component (A) are 4-15 parts by weight, 0.5-3 parts by weight, 1-15 parts by weight, and 0.25-2 parts by weight, respectively, and the ratio of components (B) and (C) is (B)/(C)=4/1.5 to 30/1.5 in weight ratio. Accordingly, excellent characteristics required for an oil hose such as oil resistance, cold resistance, and heat resistance are obtained, and a high resistance with respect to an oil having ZnDTP added thereto can be exhibited. (A) An acrylonitrile-butadiene rubber in which the amount of acrylonitrile is 26-38 wt%. (B) Zinc oxide. (C) At least one selected from the group consisting of tetramethyl thiuram disulfide, tetrabutyl thiuram disulfide, and dipentamethylene thiuram tetrasulfide. (D) An ether ester-based plasticizing agent. (E) Sulfur.

Description

オイルホースOil hose
　本発明は、建設機械（建機），鉱山（マイニング）機械向けの高圧油圧ホースや、自動車用のエンジンオイルホース等の、各種オイル輸送用ホースに用いられる、オイルホースに関するものである。 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.
　従来より、建機，マイニング機械向けの高圧油圧ホースや自動車用のエンジンオイルホース等に用いられるオイルホースにおいて、そのホース最内層の材料には、例えば、耐油性、耐熱性等に優れるアクリロニトリルブタジエンゴム等が用いられている（特許文献１～３参照）。
　一方、上記オイルホース内に流通させるオイル中には、添加剤として、ＺｎＤＴＰ（ジアルキルジチオリン酸亜鉛）が、一般に使用されている。ＺｎＤＴＰは、酸化防止能、腐食防止能、耐荷重性能、摩耗防止能等を有する工業用オイル用多機能型添加剤として広く知られている。 Conventionally, in oil hoses used for high-pressure hydraulic hoses for construction machinery and mining machines, engine oil hoses for automobiles, etc., 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).
On the other hand, ZnDTP (zinc dialkyldithiophosphate) is generally used as an additive in the oil distributed in the oil hose. 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.
特開２０１４－１８５７５８号公報Japanese Unexamined Patent Publication No. 2014-185758 特許第６００７８１８号公報Japanese Patent No. 6007818 特開２０１８－８３８９５号公報JP-A-2018-83895
　しかしながら、アクリロニトリルブタジエンゴムをポリマーとする最内層材料を用いたオイルホースは、ＺｎＤＴＰが添加されたオイルに対し、耐性が不充分になる傾向がみられるといった問題がある。
　上記の問題が発生する要因を本発明者らが調べたところ、まず、オイル中に含まれるＺｎＤＴＰは、オイルの代わりに自らが酸化され分解されて酸化防止能等を発揮するが、上記分解により、酸性物質（硫酸、硫酸亜鉛）を発生させる。そして、本発明者らは、このようにして発生した酸性物質がオイルホース内周面に接触すると、オイルホース内周面のゴムの劣化（アクリロニトリルブタジエンゴムの残存伸びの低下等）が促進されるとの知見を得た。
　また、上記最内層には、酸化劣化した上記オイルの浸透によるゴム劣化の抑制の他、耐寒性等も要求されている。
　そのため、これらの問題を改善し、ＺｎＤＴＰが添加されたオイルに対して高い耐性を示すオイルホースが求められる。 However, 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.
When the present inventors investigated the factors that cause the above problems, first, 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). Then, when the acidic substance generated in this way comes into contact with the inner peripheral surface of the oil hose, the deterioration of the rubber on the inner peripheral surface of the oil hose (decrease in the residual elongation of the acrylonitrile butadiene rubber, etc.) is promoted. I got the finding.
Further, 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.
　本発明は、このような事情に鑑みなされたもので、耐油性、耐寒性、耐熱性等の、オイルホースに要求される特性に優れるとともに、ＺｎＤＴＰが添加されたオイルに対し高い耐性を示すオイルホースを提供する。 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. Provide a hose.
　本発明者らは、前記課題を解決するため鋭意研究を重ねた。その研究の過程で本発明者らは、オイルホースの最内層材料において、そのポリマーであるアクリロニトリルブタジエンゴムに対し、酸化亜鉛、特定のチウラム系加硫促進剤、エーテルエステル系可塑剤、硫黄を、特定の割合で組合せ、さらに、上記酸化亜鉛と特定のチウラム系加硫促進剤の比率を特定の範囲にし、かつ上記アクリロニトリルブタジエンゴムとして、そのアクリロニトリル量が特定の範囲のものを用いたところ、耐油性、耐寒性、耐熱性等の要求を満たすとともに、先に述べた酸性物質（ＺｎＤＴＰの分解物）によるホース最内層の侵食を効果的に抑制することができることを見いだした。
　このような結果が得られた理由は以下のように推測される。すなわち、まず、最内層のポリマーであるアクリロニトリルブタジエンゴムのアクリロニトリル量が特定の範囲であることから、酸化劣化したオイルの浸透によるゴム劣化が抑えられる他、耐寒性等に優れるようになる。さらに、上記最内層材料中のエーテルエステル系可塑剤が、上記酸性物質により分解（上記可塑剤のエステル結合部分が分解）され、アルコール成分と、エーテル結合を有するカルボン酸成分に分解されると、上記特定のカルボン酸成分が、低分子でかつ高極性であることから、ホース内周面にブリードしやすくなる。一方、上記のような最内層材料の割合により、酸化亜鉛と特定のチウラム系加硫促進剤の分解塩（チウラムの亜鉛塩）も、上記特定のカルボン酸成分のブリードにつられて、ホース内周面付近に移行（ブルーム）しやすくなる。その結果、ホース内周面付近で、上記分解塩が、上記酸性物質の受酸成分として良好に機能するようになり、上記酸性物質によるホース最内層の侵食を効果的に抑制することができたと推測される。 The present inventors have conducted extensive research to solve the above problems. In the course of the research, 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. When a combination was made in a specific ratio, 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. It has been found that erosion of the innermost layer of the hose by the above-mentioned acidic substance (decomposed product of ZnDTP) can be effectively suppressed while satisfying the requirements of property, cold resistance, heat resistance and the like.
The reason why such a result was obtained is presumed as follows. That is, first, since the amount of acrylonitrile in the acrylonitrile butadiene rubber, which is the innermost polymer, is within a specific range, rubber deterioration due to permeation of oxidatively deteriorated oil is suppressed, and cold resistance and the like are improved. Further, when 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, Since the specific carboxylic acid component is low in molecular weight and highly polar, it easily bleeds on the inner peripheral surface of the hose. On the other hand, due to the ratio of the innermost layer material as described above, 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. As a result, 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.
　すなわち、本発明は、以下の［１］～［８］を、その要旨とする。
［１］少なくとも一層の構成層からなるオイルホースであって、その最内層が、下記（Ａ）～（Ｅ）成分を含有し、（Ａ）成分１００重量部に対して、（Ｂ）成分が４～１５重量部、（Ｃ）成分が０．５～３重量部、（Ｄ）成分が１～１５重量部、（Ｅ）成分が０．２５～２重量部であり、かつ（Ｂ）および（Ｃ）成分の割合が、重量比で、（Ｂ）／（Ｃ）＝４／１．５～３０／１．５のゴム組成物からなることを特徴とするオイルホース。
（Ａ）アクリロニトリル量が２６～３８重量％のアクリロニトリルブタジエンゴム。
（Ｂ）酸化亜鉛。
（Ｃ）テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、およびジペンタメチレンチウラムテトラスルフィドからなる群から選ばれた少なくとも一つのチウラム系加硫促進剤。
（Ｄ）エーテルエステル系可塑剤。
（Ｅ）硫黄。
［２］上記エーテルエステル系可塑剤（Ｄ）が、分子量３５０～１０００のエーテルエステル系可塑剤である、［１］に記載のオイルホース。
［３］上記ゴム組成物が、さらにカーボンブラックを、上記アクリロニトリルブタジエンゴム（Ａ）１００重量部に対して２０～７０重量部含有する、［１］または［２］に記載のオイルホース。
［４］上記ゴム組成物が、さらにシリカを、上記アクリロニトリルブタジエンゴム（Ａ）１００重量部に対して２０～６０重量部含有する、［１］～［３］のいずれかに記載のオイルホース。
［５］上記オイルホースが、複数の構成層からなり、その最内層の外周に、メッキ処理されたワイヤーからなる補強層と、上記補強層と接するゴム層とを備えている、［１］～［４］のいずれかに記載のオイルホース。
［６］上記オイルホースが、ＺｎＤＴＰを含むオイルを流通させるホースである、［１］～［５］のいずれかに記載のオイルホース。
［７］ＺｎＤＴＰを０．９重量％含む１００℃のオイルを上記ホース内に５００時間流通させたときの、上記ホース内周面から深さ１００μｍ未満までの最内層の範囲における下記（Ｘ）の値が、上記ホース内周面から深さ１００～５００μｍの最内層の範囲における下記（Ｘ）の値よりも高い、［１］～［６］のいずれかに記載のオイルホース。
（Ｘ）Ｘ線光電子分光法（ＸＰＳ）により測定される、炭素原子に対する亜鉛原子の割合（Ｚｎ／Ｃ）。
［８］上記ホース内周面から深さ１００μｍ未満までの最内層の範囲における上記（Ｘ）の値が０．０１～０．０１５であり、上記ホース内周面から深さ１００～５００μｍの最内層の範囲における上記（Ｘ）の値が０．０１未満である、［７］に記載のオイルホース。 That is, the gist of the present invention is the following [1] to [8].
[1] An oil hose composed of at least one constituent layer, wherein the innermost layer contains the following components (A) to (E), and the component (B) is contained with respect to 100 parts by weight of the component (A). 4 to 15 parts by weight, (C) component is 0.5 to 3 parts by weight, (D) component is 1 to 15 parts by weight, (E) component is 0.25 to 2 parts by weight, and (B) and An oil hose characterized in that the ratio of the component (C) is a rubber composition of (B) / (C) = 4 / 1.5 to 30 / 1.5 in terms of weight ratio.
(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.
(E) Sulfur.
[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.
[3] The oil hose according to [1] or [2], wherein the rubber composition further contains 20 to 70 parts by weight of carbon black with respect to 100 parts by weight of the acrylonitrile butadiene rubber (A).
[4] The oil hose according to any one of [1] to [3], wherein the rubber composition further contains silica in an amount of 20 to 60 parts by weight based on 100 parts by weight of the acrylonitrile butadiene rubber (A).
[5] 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].
[6] The oil hose according to any one of [1] to [5], wherein the oil hose is a hose for circulating oil containing ZnDTP.
[7] 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 μm when oil at 100 ° C. containing 0.9% by weight of ZnDTP is circulated in the hose for 500 hours. The oil hose according to any one of [1] to [6], wherein the value is higher than the value of (X) below in the range of the innermost layer having a depth of 100 to 500 μm from the inner peripheral surface of the hose.
(X) The ratio of zinc atoms to carbon atoms (Zn / C) as measured by X-ray photoelectron spectroscopy (XPS).
[8] The value of (X) in the range of the innermost layer from the inner peripheral surface of the hose to a depth of less than 100 μm is 0.01 to 0.015, and the maximum depth of 100 to 500 μm from the inner peripheral surface of the hose. The oil hose according to [7], wherein the value of (X) in the range of the inner layer is less than 0.01.
　以上のことから、本発明のオイルホースは、耐油性、耐寒性、耐熱性等の、オイルホースに要求される特性に優れるとともに、ＺｎＤＴＰが添加されたオイルに対し高い耐性を示すことができる。 From the above, 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.
本発明のオイルホースの一例を示す構成図である。It is a block diagram which shows an example of the oil hose of this invention.
　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.
　本発明のオイルホースは、先に述べたように、少なくとも一層の構成層からなるオイルホースであって、その最内層が、下記（Ａ）～（Ｅ）成分を含有し、（Ａ）成分１００重量部に対して、（Ｂ）成分が４～１５重量部、（Ｃ）成分が０．５～３重量部、（Ｄ）成分が１～１５重量部、（Ｅ）成分が０．２５～２重量部であり、かつ（Ｂ）および（Ｃ）成分の割合が、重量比で、（Ｂ）／（Ｃ）＝４／１．５～３０／１．５のゴム組成物からなる。
（Ａ）アクリロニトリル量が２６～３８重量％のアクリロニトリルブタジエンゴム（ＮＢＲ）。
（Ｂ）酸化亜鉛。
（Ｃ）テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、およびジペンタメチレンチウラムテトラスルフィドからなる群から選ばれた少なくとも一つのチウラム系加硫促進剤。
（Ｄ）エーテルエステル系可塑剤。
（Ｅ）硫黄。 As described above, 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, and the component (E) is 0.25 to parts by weight. It is composed of a rubber composition which is 2 parts by weight and the ratio of the components (B) and (C) is (B) / (C) = 4 / 1.5 to 30 / 1.5 by weight.
(A) Acrylonitrile butadiene rubber (NBR) 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.
(E) Sulfur.
　上記のように、本発明のオイルホースは、少なくとも一層の構成層からなり、その最内層が、上記に示すゴム組成物からなる。したがって、本発明のオイルホースが単層構造の場合はその層が、多層構造の場合はその最内層が、上記に示すゴム組成物からなる。
　以下、上記ゴム組成物の構成材料について詳しく説明する。 As described above, 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.
Hereinafter, the constituent materials of the rubber composition will be described in detail.
〔ＮＢＲ（Ａ）〕
　上記ＮＢＲ（Ａ）としては、そのアクリロニトリル量（ＡＮ量）が２６～３８重量％の範囲のものが用いられ、好ましくはＡＮ量が２７～３３重量％の範囲のものが用いられる。すなわち、ＮＢＲのＡＮ量が上記範囲未満であると、最内層に酸化劣化オイルが浸透しやすくなりゴム劣化しやすくなる傾向がみられるからであり、逆に、ＮＢＲのＡＮ量が上記範囲を超えると、最内層のゴム劣化とともに耐寒性等が低下する傾向がみられるからである。
　また、本発明においては、上記ゴム組成物のポリマー成分の８０重量％以上が、ＡＮ量が上記の範囲のＮＢＲ（Ａ）であることが好ましく、より好ましくは、上記ポリマー成分の９０重量％以上が、ＡＮ量が上記の範囲のＮＢＲ（Ａ）であり、さらに好ましくは上記ポリマー成分が、ＡＮ量が上記の範囲のＮＢＲ（Ａ）のみからなることである。 [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.
Further, in the present invention, 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. However, 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.
〔酸化亜鉛（Ｂ）〕
　上記酸化亜鉛（Ｂ）としては、例えば、酸化亜鉛一種、酸化亜鉛二種、酸化亜鉛三種、微細酸化亜鉛等があげられる。これらは単独でもしくは二種以上併せて用いられる。
　前記ゴム組成物における酸化亜鉛（Ｂ）の含有量は、ＮＢＲ（Ａ）１００重量部に対して、４～１５重量部の範囲であり、好ましくは７～１３重量部の範囲である。 [Zinc oxide (B)]
Examples of the zinc oxide (B) 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).
〔チウラム系加硫促進剤（Ｃ）〕
　本発明において、上記チウラム系加硫促進剤（Ｃ）としては、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、およびジペンタメチレンチウラムテトラスルフィドが、単独でもしくは二種以上併せて用いられる。すなわち、これら特定のチウラム系加硫促進剤は、他のチウラム系加硫促進剤やその他の加硫促進剤に比べ、酸化亜鉛と反応生成物である分解塩が、オイルに可溶であり、またＺｎＤＴＰの分解物である酸性物質により、エーテルエステル系可塑剤から生じるエーテル結合を有するカルボン酸成分によって、ホース内周面へブルームしやすいからである。
　前記ゴム組成物における上記チウラム系加硫促進剤（Ｃ）の含有量は、ＮＢＲ（Ａ）１００重量部に対して、０．５～３重量部の範囲であり、好ましくは１～２重量部の範囲、より好ましくは１．３～１．７重量部の範囲である。 [Thiuram-based vulcanization accelerator (C)]
In the present invention, as the 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. Further, it is because the acidic substance which is a decomposition product of ZnDTP easily blooms to the inner peripheral surface of the hose due to the carboxylic acid component having an ether bond generated from the ether ester-based plasticizing agent.
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.
　そして、前記ゴム組成物における酸化亜鉛（Ｂ）およびチウラム系加硫促進剤（Ｃ）の割合は、重量比で、（Ｂ）／（Ｃ）＝４／１．５～３０／１．５の範囲であり、好ましくは（Ｂ）／（Ｃ）＝７／１．５～１３／１．５の範囲である。
　すなわち、前記ゴム組成物において上記のような割合で酸化亜鉛（Ｂ）およびチウラム系加硫促進剤（Ｃ）を含有させると、ＺｎＤＴＰの劣化分解物（酸性物質）によるホース最内層の侵食を効果的に抑制することができるからである。 The ratio of zinc oxide (B) and thiuram-based vulcanization accelerator (C) in the rubber composition is (B) / (C) = 4 / 1.5 to 30 / 1.5 by weight. It is a range, preferably the range of (B) / (C) = 7 / 1.5 to 13 / 1.5.
That is, when zinc oxide (B) and thiuram-based vulcanization accelerator (C) are contained in the rubber composition in the above proportions, the erosion of the innermost layer of the hose by the degraded decomposition product (acidic substance) of ZnDTP is effective. This is because it can be suppressed.
〔エーテルエステル系可塑剤（Ｄ）〕
　本発明において、「エーテルエステル系可塑剤」とは、一分子中にエーテル結合とエステル結合の双方を有する可塑剤のことをいう。このような可塑剤であることから、ホース最内層中の酸化亜鉛と特定のチウラム系加硫促進剤の分解塩（チウラムの亜鉛塩）のホース内周面へのブルームが促され、ＺｎＤＴＰ分解物（酸性物質）によるホース最内層の侵食を効果的に抑制することができる。
　そして、本発明において、上記エーテルエステル系可塑剤（Ｄ）の分子量は３５０～１０００であることが好ましく、より好ましくは、上記分子量が４００～６００の範囲である。すなわち、このような低分子量の可塑剤を用いると、ＺｎＤＴＰの分解物である酸性物質により、エーテルエステル系可塑剤から生じるエーテル結合を有するカルボン酸成分によって、ホース最内層中の酸化亜鉛と特定のチウラム系加硫促進剤の分解塩（チウラムの亜鉛塩）のホース内周面へのブルームが促され、ＺｎＤＴＰ分解物（酸性物質）によるホース最内層の侵食をより効果的に抑制することができる。
　なお、上記エーテルエステル系可塑剤（Ｄ）としては、具体的には、アジピン酸ビス［２－（２－ブトキシエトキシ）エチル］等のアジピン酸エーテルエステル系可塑剤や、各種のポリエーテルエステル系可塑剤が、単独でもしくは二種以上併せて用いられる。
　また、このようなエーテルエステル系可塑剤（Ｄ）としては、市販のものでは、アデカサイザーＲＳ－１０７、アデカサイザーＲＳ－７００、アデカサイザーＲＳ－７３５、アデカサイザーＲＳ－８３０、アデカサイザーＲＳ－９６６、アデカサイザーＲＳ－１０００（以上、ＡＤＥＫＡ社製）；チオコールＴＰ－９５、チオコールＴＰ－７５９（以上、ＨＡＬＬＳＴＡＲ社製）等があげられる。 [Ether ester plasticizer (D)]
In the present invention, 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.
In the present invention, 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. ..
Specific examples of the ether ester-based plasticizer (D) 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.
In addition, as such an 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 (above, manufactured by ADEKA); thiocol TP-95, thiocol TP-759 (above, manufactured by HALLSTAR) and the like.
　前記ゴム組成物における上記エーテルエステル系可塑剤（Ｄ）の含有量は、ＮＢＲ（Ａ）１００重量部に対して、１～１５重量部の範囲であり、好ましくは３～１５重量部の範囲、より好ましくは７～１０重量部の範囲である。
　すなわち、上記エーテルエステル系可塑剤（Ｄ）の含有量が少なすぎると、ホース最内層中の酸化亜鉛と特定のチウラム系加硫促進剤の分解塩（チウラムの亜鉛塩）のホース内周面へのブルームの促進効果に乏しく、ＺｎＤＴＰ分解物（酸性物質）によるホース最内層の侵食を効果的に抑制することができないからであり、逆に上記エーテルエステル系可塑剤（Ｄ）の含有量が多すぎると、ホース内面におけるオイルからの耐油性が低下する傾向がみられるからである。 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. This is because the effect of promoting the bloom of the hose is poor, and the erosion of the innermost layer of the hose by the ZnDTP decomposition product (acidic substance) cannot be effectively suppressed. On the contrary, the content of the ether ester plasticizer (D) is high. This is because if it is too much, the oil resistance from the oil on the inner surface of the hose tends to decrease.
〔硫黄（Ｅ）〕
　上記硫黄（Ｅ）としては、例えば、粉末硫黄，沈降硫黄，不溶性硫黄といった硫黄のみならず、アルキルフェノールジスルフィド等の硫黄含有化合物を使用してもよい。これらは単独であるいは二種以上併せて用いられる。 [Sulfur (E)]
As the 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.
　上記硫黄（Ｅ）の含有量は、ＮＢＲ（Ａ）１００重量部に対して、０．２５～２重量部の範囲であり、好ましくは０．３～１．５重量部の範囲、より好ましくは０．４～０．７重量部の範囲である。
　すなわち、上記硫黄（Ｅ）の含有量が少なすぎると、架橋反応性が悪くなる傾向がみられ、逆に上記硫黄（Ｅ）の含有量が多すぎると、ゴム物性（破断強度，破断伸び）が低下する傾向がみられるからである。 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.
〔その他の最内層材料〕
　本発明のオイルホースの最内層材料である前記ゴム組成物には、上記（Ａ）～（Ｅ）成分の他、カーボンブラック、シリカ、シランカップリング剤、共架橋剤、加硫促進剤、加工助剤（ステアリン酸等）、老化防止剤、難燃剤、スコーチ防止剤等を必要に応じて配合しても差し支えない。 [Other innermost layer materials]
In addition to the above components (A) to (E), 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.
　上記カーボンブラックの含有量は、補強性の観点から、ＮＢＲ（Ａ）１００重量部に対して、２０～７０重量部の範囲であることが好ましく、より好ましくは３０～５０重量部の範囲である。 From the viewpoint of reinforcing property, 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). ..
　また、上記シリカの含有量は、耐熱老化性および酸成分の吸着の観点から、ＮＢＲ（Ａ）１００重量部に対して、２０～６０重量部の範囲であることが好ましく、より好ましくは３０～５０重量部の範囲である。 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.
　さらに、上記シリカとともに、シランカップリング剤を含有させることが、ホース最内層への酸化劣化オイルの浸透を抑え、ホース最内層の侵食をより効果的に抑制する観点から好ましい。 Further, it is preferable to contain 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.
〔本発明のオイルホースの層構成〕
　本発明のオイルホースは、先に述べたように、単層構造であっても、多層構造であってもよいが、補強性等の観点から、多層構造とすることが好ましい。そして、本発明のオイルホースは、このように複数の構成層からなり、その最内層の外周に、メッキ処理されたワイヤー（メッキワイヤー）からなる補強層と、上記補強層と接するゴム層とを備えることが好ましい（図１参照）。すなわち、上記のようにワイヤーからなる補強層を備えることが、高圧ホース用途として使用する観点から好ましく、また、防錆性等の観点から、上記のようにメッキワイヤーからなる補強層を備えることがより好ましい。 [Layer structure of oil hose of the present invention]
As described above, 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). That is, it is preferable to provide a reinforcing layer made of wire as described above from the viewpoint of use for high-pressure hoses, and from the viewpoint of rust prevention and the like, it is preferable to provide a reinforcing layer made of plated wire as described above. More preferred.
〔補強層〕
　上記補強層は、ホース全体の強度を補強するためにメッキワイヤーをブレード状、スパイラル状等に編み組してなる層である。
　上記メッキワイヤーにおけるメッキ処理としては、例えば、銅メッキ、亜鉛メッキ、黄銅（銅－亜鉛系合金）メッキ、ニッケルメッキ、錫メッキ、コバルトメッキ等があげられ、好ましくは黄銅メッキである。
　上記メッキワイヤーの直径は、通常、０．１～１．２ｍｍの範囲、好ましくは０．２～０．８ｍｍの範囲のものが用いられる。 [Reinforcing layer]
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.
〔最内層以外のゴム層〕
　なお、上記最内層以外のゴム層としては、その形成材料として、耐候性に優れたゴムが好ましく、例えば、クロロプレンゴム(ＣＲ)、スチレンブタジエンゴム（ＳＢＲ）、エチレン－プロピレン－ジエン系ゴム（ＥＰＤＭ）、ＳＢＲとＥＰＤＭのブレンドゴム、ＮＢＲとＥＰＤＭのブレンドゴム、ＮＢＲと塩化ビニル（ＰＶＣ）のブレンドゴム、アクリルゴム（ＡＣＭ）、エチレンアクリレートゴム（ＡＥＭ）、塩素化ポリエチレン（ＣＭ）、クロロスルホン化ポリエチレン（ＣＳＭ）等があげられる。これらは単独でもしくは２種以上併せて用いられる。これらのなかでも、耐候性、コスト、耐油性の点から、ＣＲが好ましい。
　また、上記の、ＣＲ等のゴム以外に、補強材（カーボンブラック等）、白色充填材、可塑剤、ステアリン酸、亜鉛華、受酸剤（高活性化マグネシウム、ハイドロタルサイト等）、老化防止剤、加硫剤、加硫剤促進剤、加工助剤等を必要に応じて適宜配合しても差し支えない。 [Rubber layer other than the innermost layer]
As the rubber layer other than the innermost layer, rubber having excellent weather resistance is preferable as the forming material thereof. For example, chloroprene rubber (CR), styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM). ), 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 Examples thereof include polyethylene (CSM). These may be used alone or in combination of two or more. Among these, CR is preferable from the viewpoint of weather resistance, cost, and oil resistance.
In addition to the above-mentioned 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.
〔オイルホースの作製〕
　本発明のオイルホースが、例えば図１に示すような層構成の場合、つぎのようにして作製することができる。すなわち、まず、最内層１用材料として、前記（Ａ）～（Ｅ）成分の各成分材料を準備し、必要に応じてその他の成分材料も準備し、これらをロール、ニーダー、バンバリーミキサー等の混練機を用いて混練することにより、最内層１形成用のゴム組成物を調製する。ついで、押出成形機を用いて、上記最内層１形成用のゴム組成物をマンドレル上に押し出して最内層１を成形する。つぎに、上記最内層１の外周面に、編組機を用いて、メッキワイヤーをスパイラル状に編み組して補強層２を形成する。その後、上記補強層２の外周面に、外層３形成用のゴム組成物を押し出して外層３を形成する。このようにして得られたホース状積層体（未加硫）を、所定の条件（例えば、１４０～１７０℃×１０～６０分間）で加硫することにより、最内層１／補強層２／外層３の順に一体形成されてなるホース（本発明のオイルホース）を得ることができる（図１参照）。 [Making an oil hose]
When 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. Next, 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. After that, 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. By vulcanizing the hose-shaped laminate (unvulcanized) thus obtained under predetermined conditions (for example, 140 to 170 ° C. × 10 to 60 minutes), the innermost layer 1 / reinforcing layer 2 / outer layer A hose (oil hose of the present invention) integrally formed in the order of 3 can be obtained (see FIG. 1).
　本発明のオイルホースにおいて、ホース内径は、通常、３～１００ｍｍの範囲、好ましくは６～６５ｍｍの範囲であり、ホース外径は、通常、７～１５０ｍｍの範囲、好ましくは１０～９０ｍｍの範囲である。 In the oil hose of the present invention, 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.
　また、最内層１の厚みは、通常、０．６～４ｍｍの範囲、好ましくは１～３ｍｍの範囲である。外層３の厚みは、通常、０．２～４ｍｍの範囲、好ましくは０．６～３ｍｍの範囲である。 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.
　なお、本発明のオイルホースは、図１に示したような三層構造に限定されるものではなく、最内層１のみからなる単層構造のものや、最内層１の外周に補強層２または外層３のみが積層された二層構造のものであってもよい。また、上記補強層２と外層３とを交互に二層以上積層した構造であってもよい。
　また、上記補強層２のようなワイヤー層や、上記外層３のような、最内層１とは異なるゴム層の他、必要に応じ、樹脂層や補強糸層等を、上記最内層１の外周に形成してもよい。 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.
　上記のようにして得られる本発明のオイルホースは、ＺｎＤＴＰを０．９重量％含む１００℃のオイルを上記ホース内に５００時間流通させたときの、上記ホース内周面から深さ１００μｍ未満までの最内層の範囲における下記（Ｘ）の値が、上記ホース内周面から深さ１００～５００μｍの最内層の範囲における下記（Ｘ）の値よりも高いものであることが望ましい。そして、上記の条件において、上記ホース内周面から深さ１００μｍ未満までの最内層の範囲における下記（Ｘ）の値が０．０１～０．０１５（より好ましくは０．０１１～０．０１５、さらに好ましくは０．０１３～０．０１５）であり、上記ホース内周面から深さ１００～５００μｍの最内層の範囲における下記（Ｘ）の値が０．０１未満（より好ましくは０．００９未満、さらに好ましくは０．００７未満）であることが、より望ましい。
（Ｘ）Ｘ線光電子分光法（ＸＰＳ）により測定される、炭素原子に対する亜鉛原子の割合（Ｚｎ／Ｃ）。
　すなわち、上記のような要件を満たすものであると、ＺｎＤＴＰの分解物（酸性物質）によるホース最内層の侵食を効果的に抑制することができるからである。
　なお、上記ＸＰＳによる、炭素原子に対する亜鉛原子の割合（Ｚｎ／Ｃ）の測定は、例えば、以下の条件により測定される。
≪ＸＰＳ測定条件≫
　測定装置：ＰＨＩ５０００　ＶｅｒｓａＰｒｏｂｅ　II（アルバック・ファイ社製）
　照射Ｘ線：Ａｌ　Ｋα単色化Ｘ線
　出力：２５Ｗ、１５ｋＶ
　光電子取り出し角度：４５度
　帯電中和：Ａｒイオンビーム、および電子ビーム
　分析エリア：スポット分析（１００μｍφ） The oil hose of the present invention obtained as described above has a depth of less than 100 μm 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 μm from the inner peripheral surface of the hose. Under the above conditions, 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 μm 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 μm 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).
That is, if the above requirements are satisfied, erosion of the innermost layer of the hose by the decomposition product (acidic substance) of ZnDTP can be effectively suppressed.
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 Kα Monochromatic X-ray Output: 25W, 15kV
Photoelectron extraction angle: 45 degrees Charge neutralization: Ar ion beam and electron beam Analysis area: Spot analysis (100 μmφ)
　そして、本発明のオイルホースは、特に、ＺｎＤＴＰを含むオイルを流通させるホースとして好ましく用いられるが、ＺｎＤＴＰを含まないオイルを流通させるホースとしても用いることができる。また、本発明のオイルホースは、耐圧性が要求されるホース全般に使用可能であり、例えば、建機、マイニング機械、産業車両（フォークリフト、無人搬送車等）、自動車用のエンジンオイルホース等に使用できる。そして、特に建機やマイニング機械向けの高圧油圧ホースとして好適に用いられる。 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.
　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, the materials shown below were prepared prior to the examples and comparative examples.
〔ＮＢＲ（ｉ）〕
　ニポールＤＮ３０２、日本ゼオン社製、ＡＮ量：２７．５重量％ [NBR (i)]
Nipole DN302, manufactured by Zeon Corporation, AN amount: 27.5% by weight
〔ＮＢＲ（ii）〕
　ニポールＤＮ２０２、日本ゼオン社製、ＡＮ量：３１．０重量％ [NBR (ii)]
Nipole DN202, manufactured by Zeon Corporation, AN amount: 31.0% by weight
〔ＮＢＲ（iii）〕
　ＪＳＲ　Ｎ２３０Ｓ、ＪＳＲ社製、ＡＮ量：３５．０重量％ [NBR (iii)]
JSR N230S, manufactured by JSR, AN amount: 35.0% by weight
〔ＮＢＲ（iv）〕
　ニポールＤＮ４０１、日本ゼオン社製、ＡＮ量：１８．０重量％ [NBR (iv)]
Nipole DN401, manufactured by Zeon Corporation, AN amount: 18.0% by weight
〔ＮＢＲ（v）〕
　ニポールＤＮ４０５０、日本ゼオン社製、ＡＮ量：４０．０重量％ [NBR (v)]
Nipole DN4050, manufactured by Zeon Corporation, AN amount: 40.0% by weight
〔酸化亜鉛〕
　酸化亜鉛二種、堺化学社製 [Zinc oxide]
Two types of zinc oxide, manufactured by Sakai Chemical Co., Ltd.
〔ステアリン酸〕
　ルナック　Ｓ－７０Ｖ、花王社製 〔stearic acid〕
Lunac S-70V, manufactured by Kao Corporation
〔老化防止剤（ｉ）〕
　２，２，４－トリメチル－１，２－ジヒドロキノリン重合体 [Anti-aging agent (i)]
2,2,4-trimethyl-1,2-dihydroquinoline polymer
〔老化防止剤（ii）〕
　９，１０－ジヒドロ－９，９－ジメチルアクリジン [Anti-aging agent (ii)]
9,10-dihydro-9,9-dimethylacridine
〔カーボンブラック〕
　シーストＳＯ、東海カーボン社製 〔Carbon black〕
Seest SO, manufactured by Tokai Carbon Co., Ltd.
〔シリカ〕
　ニプシールＥＲ、東ソー・シリカ社製 〔silica〕
Nipseal ER, manufactured by Tosoh Silica
〔エーテルエステル系可塑剤〕
　アデカサイザーＲＳ－１０７、ＡＤＥＫＡ社製、分子量：４３４ [Ether ester plasticizer]
ADEKA Sizer RS-107, manufactured by ADEKA, molecular weight: 434
〔エーテル系可塑剤〕
　チオコールＴＰ－９０Ｂ、ＨＡＬＬＳＴＡＲ社製 [Ether plasticizer]
Thiocol TP-90B, manufactured by HALLSTAR
〔エステル系可塑剤〕
　ＤＯＡ、田岡化学社製 [Ester plasticizer]
DOA, manufactured by Taoka Chemical Co., Ltd.
〔チウラム系加硫促進剤（ｉ）〕
　ノクセラーＴＥＴ（テトラエチルチウラムジスルフィド）、大内新興化学社製 [Thiuram-based vulcanization accelerator (i)]
Noxeller TET (Tetraethyl Thiram Disulfide), manufactured by Ouchi Shinko Kagaku Co., Ltd.
〔チウラム系加硫促進剤（ii）〕
　ノクセラーＴＢＴ（テトラブチルチウラムジスルフィド）、大内新興化学社製 [Thiuram-based vulcanization accelerator (ii)]
Noxeller TBT (Tetrabutyl Thiram Disulfide), manufactured by Ouchi Shinko Kagaku Co., Ltd.
〔チウラム系加硫促進剤（iii）〕
　ノクセラーＴＲＡ（ジペンタメチレンチウラムテトラスルフィド）、大内新興化学社製 [Thiuram-based vulcanization accelerator (iii)]
Noxeller TRA (dipentamethylene thiuram tetrasulfide), manufactured by Ouchi Shinko Kagaku Co., Ltd.
〔チウラム系加硫促進剤（iv）〕
　ノクセラーＴＢＺＴＤ（テトラベンジルチウラムジスルフィド）、大内新興化学社製 [Thiuram-based vulcanization accelerator (iv)]
Noxeller TBZTD (Tetrabenzyl Thiram Disulfide), manufactured by Ouchi Shinko Kagaku Co., Ltd.
〔チウラム系加硫促進剤（ｖ）〕
　ノクセラーＴＯＴ－Ｎ（テトラキス（２－エチルヘキシル）チウラムジスルフィド）、大内新興化学社製 [Thiuram-based vulcanization accelerator (v)]
Noxeller TOT-N (Tetrakis (2-ethylhexyl) thiuram disulfide), manufactured by Ouchi Shinko Kagaku Co., Ltd.
〔スルフェンアミド系加硫促進剤〕
　ノクセラーＭＳＡ、大内新興化学社製 [Sulfenamide-based vulcanization accelerator]
Noxeller MSA, manufactured by Ouchi Shinko Kagaku Co., Ltd.
〔加硫剤〕
　硫黄 [Vulcanizing agent]
sulfur
〔スコーチ防止剤〕
　リターダーＣＴＰ、東レ社製 [Scorch inhibitor]
Retarder CTP, manufactured by Toray Industries, Inc.
［実施例１～１７、比較例１～１２］
　上記各材料を、後記の表１～３に示す割合で混練して、ゴム組成物を調製した。なお、上記混練は、まず、加硫剤と加硫促進剤以外の材料を、バンバリーミキサーを用いて混練し、ついで、加硫剤と加硫促進剤を配合し、オープンロールを用いて混練することにより行った。
　そして、上記ゴム組成物を押出成形したものにマンドレルを挿入し、１５０℃×６０分間でスチーム加硫し、厚み５ｍｍのオイルホース(内径１２ｍｍ)を作製した。 [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. In the above kneading, first, 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.
Then, 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.
　そして、上記各オイルホースに関し、下記の方法に従って各種特性を測定・評価した。これらの結果を、後記の表１～３に併せて示した。 Then, for each of the above oil hoses, various characteristics were measured and evaluated according to the following method. These results are also shown in Tables 1 to 3 below.
＜常態時物性＞
　各オイルホースから切り出した試験片に対して、ＪＩＳ　Ｋ　６２５１：２０１０に準拠し、引張り強さ〔ＴＢ：破断点強度（ＭＰａ）〕、伸び〔ＥＢ：破断点伸び（％）〕をそれぞれ測定した。また、ＪＩＳ　Ｋ　６２５３－３：２０１２に準拠し、試験片の硬さ（Ｈｓ：ＪＩＳ　Ａ）も測定した。
　そして、以下の基準で常態時物性の評価を行った。
　○：伸び２００％以上。
　×：伸び２００％未満。 <Physical characteristics under normal conditions>
Tensile strength [TB: breaking point strength (MPa)] and elongation [EB: breaking point elongation (%)] were measured for each test piece cut out from each oil hose in accordance with JIS K 6251: 2010. .. In addition, the hardness (Hs: JIS A) of the test piece was also measured according to JIS K 6253-3: 2012.
Then, the physical characteristics under normal conditions were evaluated according to the following criteria.
◯: Growth of 200% or more.
X: Growth is less than 200%.
＜耐油性＞
　各オイルホースから切り出した試験片に対して、ＪＩＳ　Ｋ　６２５８：２０１０に準拠し、試験液「ＣＦ－３０」（ＪＸ日鉱日石エネルギー社製のディーゼルエンジンオイル）に浸漬し、１３５℃×４８０時間加熱して、試験液中のＺｎＤＴＰ分解物により酸劣化させる試験を行った。
　その後、ＪＩＳ　Ｋ　６２５１：２０１０に準拠し、上記試験片の伸び（残存伸び（％））を測定した。そして、先に測定した常態時物性の伸び（初期の伸び）との差から、酸劣化試験後の伸びの減少割合（ΔＥＢ（％））を算出した。
　そして、以下の基準で耐油性の評価を行った。
　○：残存伸び８０％以上。
　×：残存伸び８０％未満。 <Oil resistance>
The 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. Then, the rate of decrease in elongation (ΔEB (%)) 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%.
＜耐寒性＞
　各オイルホースから切り出した試験片に対して、ＪＩＳ　Ｋ　６２６１：２００６に規定する低温衝撃脆化試験に準拠し、低温脆化温度（℃）を測定した。
　そして、以下の基準で耐寒性の評価を行った。
　○：－３０℃以下。
　△：－３０℃よりも高く－２０℃よりも低い。
　×：－２０℃以上。 <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.
Δ: Higher than -30 ° C and lower than -20 ° C.
X: -20 ° C or higher.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記表１および表２の結果から、全実施例のオイルホースは、常態時物性、耐油性、耐寒性に関し、優れた結果が得られた。 From the results in Tables 1 and 2 above, the oil hoses of all the examples obtained excellent results in terms of physical characteristics, oil resistance, and cold resistance under normal conditions.
　これに対して、上記表３の結果から、比較例１では、チウラム系加硫促進剤の割合が少な過ぎ、ＺｎＤＴＰ分解物によるゴムの酸劣化を抑えるのに充分なチウラムの亜鉛塩がブルームしなかったため、耐油性に劣る結果となった。比較例２では、チウラム系加硫促進剤の割合が多過ぎ、常態時伸びが小さくなったことに伴い、ＣＦ－３０に浸漬後の残存伸びも小さくなったため、常態時物性、耐油性に悪影響が及んだ。
　比較例３では、酸化亜鉛の割合が少な過ぎ、ＺｎＤＴＰ分解物によるゴムの酸劣化を抑えるのに充分なチウラムの亜鉛塩がブルームしなかったため、耐油性に劣る結果となった。比較例４では、酸化亜鉛の割合が多過ぎ、ゴム自体が脆くなったため、耐油性に劣る結果となった。
　比較例５では、エーテルエステル系可塑剤の割合が多過ぎ、オイルがゴムに浸透しやすくなったため、耐油性に劣る結果となった。
　比較例１２では、エーテルエステル系可塑剤の配合量が充分でないため、ＺｎＤＴＰ分解物によるゴムの酸劣化を抑えるのに充分なチウラムの亜鉛塩のブルームが促進されなかったため、耐油性に劣る結果となった。
　比較例６では、エーテルエステル系可塑剤に代えてエーテル系可塑剤を含有しており、ＺｎＤＴＰ分解物によるゴムの酸劣化を抑えるのに充分なチウラムの亜鉛塩のブルームが促進されなかったため、耐油性に劣る結果となった。比較例７では、エーテルエステル系可塑剤に代えてエステル系可塑剤を含有しており、ＺｎＤＴＰ分解物によるゴムの酸劣化を抑えるのに充分なチウラムの亜鉛塩のブルームが促進されなかったため、比較例６と同様に、耐油性に劣る結果となった。
　比較例８では、ＮＢＲのＡＮ量が低過ぎ、耐油性に劣る結果となった。比較例９では、ＮＢＲのＡＮ量が高過ぎ、耐寒性等に劣る結果となった。
　比較例１０および１１では、本発明に使用されるものとは異なるチウラム系加硫促進剤を使用しており、本発明に要求される所望の耐油性（耐酸劣化性）を得ることができなかった。 On the other hand, from the results in Table 3 above, in 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. In 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.
In 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. In Comparative Example 4, the proportion of zinc oxide was too large and the rubber itself became brittle, resulting in inferior oil resistance.
In 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.
In 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. became.
In Comparative Example 6, an ether-based plasticizer was contained instead of the ether-based plasticizer, and 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, so that the oil resistance was not increased. The result was inferior in sex. In Comparative Example 7, an ester-based plasticizer was contained instead of the ether-based plasticizer, and 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. As in Example 6, the result was that the oil resistance was inferior.
In Comparative Example 8, the AN amount of NBR was too low, resulting in poor oil resistance. In Comparative Example 9, the AN amount of NBR was too high, resulting in inferior cold resistance and the like.
In 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.
　また、全実施例のオイルホースに関し、その外周に、メッキ処理されたワイヤーからなる補強層と、上記補強層と接するゴム層とを形成したところ（図１参照）、高圧ホース用途として優れた性能を示すことを確認した。 Further, regarding the oil hoses of all the examples, when a reinforcing layer made of plated wire and a rubber layer in contact with the reinforcing layer are formed on the outer periphery thereof (see FIG. 1), excellent performance as a high-pressure hose application. It was confirmed that
　さらに、実施例２および実施例６のオイルホースに対し、ＺｎＤＴＰを０．９重量％含む１００℃のオイルを上記ホース内に５００時間流通させた後、上記ホースの最内層から試験片を切り出し、以下の測定を行った。
　すなわち、上記試験片に対し、下記のＸＰＳ測定条件により、上記ホースの内周面からの深さ０μｍ（内周面）、８０μｍ、１００μｍ、２００μｍ、５００μｍにおける、炭素原子に対する亜鉛原子の割合（Ｚｎ／Ｃ）を測定した。測定結果は、下記の表４に示す。
≪ＸＰＳ測定条件≫
　測定装置：ＰＨＩ５０００　ＶｅｒｓａＰｒｏｂｅ　II（アルバック・ファイ社製）
　照射Ｘ線：Ａｌ　Ｋα単色化Ｘ線
　出力：２５Ｗ、１５ｋＶ
　光電子取り出し角度：４５度
　帯電中和：Ａｒイオンビーム、および電子ビーム
　分析エリア：スポット分析（１００μｍφ） Further, with respect to the oil hoses of Examples 2 and 6, 100 ° C. oil containing 0.9% by weight of ZnDTP was circulated in the hose for 500 hours, and then a test piece was cut out from the innermost layer of the hose. The following measurements were made.
That is, the ratio of zinc atoms to carbon atoms (Zn) at depths of 0 μm (inner peripheral surface), 80 μm, 100 μm, 200 μm, and 500 μm from the inner peripheral surface of the hose with respect to the test piece under the following XPS measurement conditions. / C) was measured. The measurement results are shown in Table 4 below.
≪XPS measurement conditions≫
Measuring device: PHI5000 VersaProbe II (manufactured by ULVAC-PHI)
Irradiation X-ray: Al Kα Monochromatic X-ray Output: 25W, 15kV
Photoelectron extraction angle: 45 degrees Charge neutralization: Ar ion beam and electron beam Analysis area: Spot analysis (100 μmφ)
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上記表４に示すように、実施例２では、Ｚｎ／Ｃの値が、深さ１００μｍ未満までは０．０１～０．０１５の範囲内にあり、深さ１００μｍ～５００μｍでは０．０１未満である。これに対し、実施例６では、Ｚｎ／Ｃの値が、深さ１００μｍ未満までは０．０１～０．０１５の範囲内にあるが、深さ１００μｍ～５００μｍでは０．０１以上である。
　実施例２および実施例６のオイルホースは、前記表１からも明らかなように、材料組成が互いに非常に近いが、実施例２のほうが耐油性等の評価に優れる結果となっている。この結果は、上記表４に示されるＺｎ／Ｃの値の違いによるものと考えられる。 As shown in Table 4 above, in Example 2, the Zn / C value is in the range of 0.01 to 0.015 up to a depth of less than 100 μm, and less than 0.01 at a depth of 100 μm to 500 μm. is there. On the other hand, in Example 6, the Zn / C value is in the range of 0.01 to 0.015 up to a depth of less than 100 μm, but is 0.01 or more at a depth of 100 μm to 500 μm.
As is clear from Table 1 above, 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.
　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。当業者に明らかな様々な変形は、本発明の範囲内であることが企図されている。 Although the specific embodiment of the present invention has been shown in the above examples, the above examples are merely examples and are not interpreted in a limited manner. Various variations apparent to those skilled in the art are intended to be within the scope of the present invention.
　本発明のオイルホースは、各種オイル輸送用ホースに用いられるホースであって、耐圧性が要求されるホース全般に使用可能である。例えば、建機、マイニング機械、産業車両（フォークリフト、無人搬送車等）、自動車用のエンジンオイルホース等に使用でき、特に建機やマイニング機械向けの高圧油圧ホースとして好適に用いられる。 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. For example, 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.
　１　最内層
　２　補強層
　３　外層 1 Inner layer 2 Reinforcement layer 3 Outer layer

Claims (8)

  1. 　少なくとも一層の構成層からなるオイルホースであって、その最内層が、下記（Ａ）～（Ｅ）成分を含有し、（Ａ）成分１００重量部に対して、（Ｂ）成分が４～１５重量部、（Ｃ）成分が０．５～３重量部、（Ｄ）成分が１～１５重量部、（Ｅ）成分が０．２５～２重量部であり、かつ（Ｂ）および（Ｃ）成分の割合が、重量比で、（Ｂ）／（Ｃ）＝４／１．５～３０／１．５のゴム組成物からなることを特徴とするオイルホース。
    （Ａ）アクリロニトリル量が２６～３８重量％のアクリロニトリルブタジエンゴム。
    （Ｂ）酸化亜鉛。
    （Ｃ）テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、およびジペンタメチレンチウラムテトラスルフィドからなる群から選ばれた少なくとも一つのチウラム系加硫促進剤。
    （Ｄ）エーテルエステル系可塑剤。
    （Ｅ）硫黄。     An oil hose composed of at least one constituent layer, the innermost layer containing the following components (A) to (E), and the component (B) is 4 to 15 with respect to 100 parts by weight of the component (A). 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 2 parts by weight, and (B) and (C). An oil hose having a rubber composition in which the ratio of components is (B) / (C) = 4 / 1.5 to 30 / 1.5 in terms of weight ratio.
    (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.
    (E) Sulfur.
  2. 　上記エーテルエステル系可塑剤（Ｄ）が、分子量３５０～１０００のエーテルエステル系可塑剤である、請求項１記載のオイルホース。 The oil hose according to claim 1, wherein the ether ester-based plasticizer (D) is an ether ester-based plasticizer having a molecular weight of 350 to 1000.
  3. 　上記ゴム組成物が、さらにカーボンブラックを、上記アクリロニトリルブタジエンゴム（Ａ）１００重量部に対して２０～７０重量部含有する、請求項１または２記載のオイルホース。 The oil hose according to claim 1 or 2, wherein the rubber composition further contains 20 to 70 parts by weight of carbon black with respect to 100 parts by weight of the acrylonitrile butadiene rubber (A).
  4. 　上記ゴム組成物が、さらにシリカを、上記アクリロニトリルブタジエンゴム（Ａ）１００重量部に対して２０～６０重量部含有する、請求項１～３のいずれか一項に記載のオイルホース。 The oil hose according to any one of claims 1 to 3, wherein the rubber composition further contains silica in an amount of 20 to 60 parts by weight based on 100 parts by weight of the acrylonitrile butadiene rubber (A).
  5. 　上記オイルホースが、複数の構成層からなり、その最内層の外周に、メッキ処理されたワイヤーからなる補強層と、上記補強層と接するゴム層とを備えている、請求項１～４のいずれか一項に記載のオイルホース。 Any of claims 1 to 4, wherein the oil hose is composed of a plurality of constituent layers, and has a reinforcing layer made of a plated wire and a rubber layer in contact with the reinforcing layer on the outer periphery of the innermost layer thereof. The oil hose described in item 1.
  6. 　上記オイルホースが、ジアルキルジチオリン酸亜鉛を含むオイルを流通させるホースである、請求項１～５のいずれか一項に記載のオイルホース。 The oil hose according to any one of claims 1 to 5, wherein the oil hose is a hose for circulating oil containing zinc dialkyldithiophosphate.
  7. 　ジアルキルジチオリン酸亜鉛を０．９重量％含む１００℃のオイルを上記ホース内に５００時間流通させたときの、上記ホース内周面から深さ１００μｍ未満までの最内層の範囲における下記（Ｘ）の値が、上記ホース内周面から深さ１００～５００μｍの最内層の範囲における下記（Ｘ）の値よりも高い、請求項１～６のいずれか一項に記載のオイルホース。
    （Ｘ）Ｘ線光電子分光法（ＸＰＳ）により測定される、炭素原子に対する亜鉛原子の割合（Ｚｎ／Ｃ）。     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 μm when oil at 100 ° C. containing 0.9% by weight of zinc dialkyldithiophosphate was circulated in the hose for 500 hours. The oil hose according to any one of claims 1 to 6, wherein the value is higher than the value of (X) below in the range of the innermost layer having a depth of 100 to 500 μm from the inner peripheral surface of the hose.
    (X) The ratio of zinc atoms to carbon atoms (Zn / C) as measured by X-ray photoelectron spectroscopy (XPS).
  8. 　上記ホース内周面から深さ１００μｍ未満までの最内層の範囲における上記（Ｘ）の値が０．０１～０．０１５であり、上記ホース内周面から深さ１００～５００μｍの最内層の範囲における上記（Ｘ）の値が０．０１未満である、請求項７記載のオイルホース。 The value of (X) in the range of the innermost layer from the inner peripheral surface of the hose to a depth of less than 100 μm is 0.01 to 0.015, and the range of the innermost layer having a depth of 100 to 500 μm from the inner peripheral surface of the hose. The oil hose according to claim 7, wherein the value of (X) above is less than 0.01.
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