WO2022113671A1 - Composition de caoutchouc pour tubes internes de tuyau, et tuyau - Google Patents

Composition de caoutchouc pour tubes internes de tuyau, et tuyau Download PDF

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Publication number
WO2022113671A1
WO2022113671A1 PCT/JP2021/040445 JP2021040445W WO2022113671A1 WO 2022113671 A1 WO2022113671 A1 WO 2022113671A1 JP 2021040445 W JP2021040445 W JP 2021040445W WO 2022113671 A1 WO2022113671 A1 WO 2022113671A1
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mass
rubber
parts
rubber composition
hose
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PCT/JP2021/040445
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English (en)
Japanese (ja)
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拓也 上村
克徳 紺谷
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株式会社ブリヂストン
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Priority to JP2022565169A priority Critical patent/JPWO2022113671A1/ja
Publication of WO2022113671A1 publication Critical patent/WO2022113671A1/fr

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    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
    • 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
    • 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
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/34—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
    • C08K5/16—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
    • C08K5/3415—Five-membered 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
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/44—Sulfenamides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall

Definitions

  • the present invention relates to a rubber composition for an inner hose pipe, a rubber-metal composite, a conveyor belt, a hose, a crawler and a tire.
  • rubber products such as hoses have been composed of composite materials using metal reinforcing materials such as wires because of their required pressure resistance characteristics.
  • metal reinforcing materials such as wires because of their required pressure resistance characteristics.
  • this metal reinforcing material exerts a high reinforcing effect, so that peeling between the metal reinforcing material and the rubber member is suppressed in order to ensure higher reliability as a product.
  • Highly stable adhesiveness inner tube peeling resistance
  • a method of bonding the above-mentioned metal reinforcing material and the rubber member a method of simultaneously bonding the rubber and the metal, a so-called direct vulcanization bonding method, is known, and among the direct vulcanization bonding methods.
  • Sulfur amide-based vulcanization accelerator which gives a delayed effect to the vulcanization reaction, is useful for simultaneously performing vulcanization of rubber and bonding with a metal.
  • Examples of the vulcanization accelerator currently on the market that gives a slow-acting effect to the vulcanization reaction include N, N'-dicyclohexyl-2-benzothiazolylsulfenamide, and further, the slow-acting agent is required.
  • Patent Document 1 discloses a technique for containing a specific sulfenamide-based vulcanization accelerator in a rubber composition.
  • a technique of blending cobalt chloride into a rubber composition is known as a technique for improving the peel resistance of the inner tube of a rubber member.
  • cobalt chloride By acting as an adhesive promoter, cobalt chloride can improve the peel resistance of the inner tube of the rubber member.
  • the demand for environmentally friendly materials has been increasing, and the development of a technique capable of improving the peel resistance of the inner tube without using cobalt chloride is being promoted.
  • a technique of blending a large amount of a filler in the rubber composition is known as a technique capable of enhancing the peeling resistance of the inner tube separately from the above-mentioned adhesion accelerator.
  • a filler of silica or carbon black By blending a filler of silica or carbon black into the rubber composition, the viscosity of the vulcanized rubber can be increased and the adhesiveness with the metal member can be enhanced.
  • the viscosity of the rubber composition becomes too high, so that the processability is lowered and sufficient productivity cannot be obtained.
  • an object of the present invention is to provide a rubber composition for a hose inner tube that can realize excellent inner tube peeling resistance and productivity even when the cobalt compound is not contained or the content is small. ..
  • Another object of the present invention is to provide a laminate and a hose having excellent inner tube peeling resistance and productivity even when the cobalt compound is not contained or the content is small. ..
  • the gist of the present invention for solving the above-mentioned problems is as follows.
  • the rubber composition for an inner pipe of a hose of the present invention is a rubber composition for an inner pipe of a hose.
  • a cobalt compound is contained as an optional component, and the content of the cobalt compound is 0.1% by mass or less with respect to the entire rubber composition for the inner hose pipe in terms of the amount of cobalt. It is characterized by not containing a thiazole-based vulcanization accelerator.
  • the silica is contained in an amount of 2 parts by mass or more with respect to 100 parts by mass of the rubber component. This is because better inner tube peeling resistance can be realized.
  • the rubber composition for inner hose pipe of the present invention it is preferable to further contain 1.5 parts by mass or less of the vulcanization retarder as an essential component with respect to 100 parts by mass of the rubber component. This is because better inner tube peeling resistance can be realized.
  • the rubber composition for an inner hose of the present invention contains 2.0 parts by mass or more of a vulcanization accelerator other than the thiazole-based vulcanization accelerator with respect to 100 parts by mass of the rubber component. This is because better inner tube peeling resistance can be realized.
  • the vulcanization accelerator other than the thiazole-based vulcanization accelerator is a sulfenamide-based vulcanization accelerator. This is because better inner tube peeling resistance can be realized.
  • the rubber composition for an inner hose tube of the present invention preferably further contains less than 120 parts by mass of carbon black as an essential component with respect to 100 parts by mass of the rubber component, and may contain 60 parts by mass or more and 110 parts by mass or less. More preferred. This is because better inner tube peeling resistance can be achieved without reducing productivity.
  • the carbon black preferably contains at least one carbon black selected from FEF, GPF and SRF, and the carbon black is the carbon black of FEF. It is more preferably contained at least, and the content thereof is 70 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the rubber component. This is because better inner tube peeling resistance can be achieved without reducing productivity.
  • the laminate of the present invention is characterized by comprising a layer made of a vulcanized product of the rubber composition for an inner hose tube of the present invention described above, and a brass-plated wire.
  • the hose of the present invention is characterized by having a laminate of the present invention arranged on the inner side in the radial direction of the hose and an outer skin rubber layer arranged on the outermost side in the radial direction of the hose.
  • the present invention it is possible to provide a rubber composition for a hose inner tube that can realize excellent inner tube peeling resistance and productivity even when the cobalt compound is not contained or the content is small. Further, according to the present invention, it is possible to provide a laminate and a hose having excellent inner tube peeling resistance and productivity even when the cobalt compound is not contained or the content is small.
  • the rubber composition for an inner tube of a hose of the present invention is a rubber composition (rubber composition for an inner tube) used for an inner tube of a hose.
  • rubber composition for an inner tube As an essential component for 100 parts by mass of rubber component A) 20 parts by mass or less of butadiene rubber, B) 80 parts by mass or more of acrylonitrile butadiene rubber, C) Less than 10 parts by mass of silica, D) Contains 3.0 parts by mass or less of a vulcanization accelerator other than thiazole.
  • the rubber composition for an inner tube to be bonded to a metal member such as a brass-plated wire contains the above-mentioned A) butadiene rubber and B) acrylonitrile butadiene rubber as rubber components, and is added other than C) silica and D) thiazole.
  • a specific amount of the sulfurization accelerator it becomes possible to enhance the peel resistance of the inner tube due to these synergistic effects.
  • the viscosity of the rubber composition is reduced and the productivity is also improved. Can be done.
  • the rubber composition for an inner hose pipe of the present invention contains a rubber component.
  • A) butadiene rubber of 20 parts by mass or less and B) acrylonitrile butadiene rubber of 80 parts by mass or more are contained with respect to 100 parts by mass of the rubber component.
  • the A) butadiene rubber not only polybutadiene rubber (PBR) but also butadiene rubber such as syndiotactic 1,2-polybutadiene (sPB) and high cis-butadiene rubber (high cis BR) can be used. It is possible. Only one kind of these butadiene rubbers can be used, or a plurality of kinds of butadiene rubbers can be mixed and used.
  • the content of the A) butadiene rubber is preferably 20 parts by mass or less with respect to 100 parts by mass of the rubber component from the viewpoint of ensuring a balance between inner tube peel resistance and productivity.
  • the content of B) acrylonitrile butadiene rubber (NBR) needs to be 80 parts by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of enhancing the inner tube peeling resistance and oil resistance. Further, from the viewpoint of low temperature resistance, the content of B) acrylonitrile butadiene rubber (NBR) is preferably 85 parts by mass or less.
  • the B) acrylonitrile butadiene rubber may contain two or more types of NBR. In that case, 30 to 60 parts by mass of a so-called high acrylonitrile butadiene rubber having a nitrile content (AN content) of 40 to 45, and 20 to 50 parts by mass of a so-called medium-high acrylonitrile butadiene rubber having a nitrile content (AN content) of 30 to 40. It is preferable to include it. By blending two types of B) acrylonitrile butadiene rubber, it is possible to obtain a hose inner tube rubber having excellent physical properties such as oil resistance and cold resistance.
  • the rubber component may also contain a rubber component (other rubber components) other than the above-mentioned A) butadiene rubber and B) acrylonitrile butadiene rubber.
  • a rubber component other rubber components
  • the other rubber components include natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), ethylene propylene diene rubber (EPDM), and chloroprene rubber (CR).
  • NR natural rubber
  • IR isoprene rubber
  • SBR styrene butadiene rubber
  • SIBR styrene isoprene butadiene rubber
  • EPDM ethylene propylene diene rubber
  • CR chloroprene rubber
  • Butyl rubber (IIR) modified products thereof and the like can be used.
  • the rubber composition for an inner hose tube of the present invention contains C) silica of less than 10 parts by mass with respect to 100 parts by mass of the rubber component as a filler.
  • C) silica as a filler, the adhesiveness of the rubber composition can be enhanced and the peel resistance of the inner tube can be improved.
  • the type of silica is not particularly limited.
  • wet silica hydrous silicic acid
  • dry silica anhydrous silicic acid
  • calcium silicate aluminum silicate and the like
  • the BET specific surface area (measured based on ISO5794 / 1) of the wet silica is preferably about 100 to 300 m 2 / g.
  • Silica having a BET specific surface area in this range can further improve the inner tube peel resistance without lowering the productivity.
  • the silica may be used alone or in combination of two or more.
  • the content of the silica is less than 10 parts by mass with respect to 100 parts by mass of the rubber component.
  • the content of the silica is 10 parts by mass or more with respect to 100 parts by mass of the rubber component, the viscosity of the rubber composition may increase and the productivity may decrease.
  • the content of the silica is preferably 9 parts by mass or less, and more preferably 7 parts by mass or less with respect to 100 parts by mass of the rubber component.
  • the content of the silica is preferably 2 parts by mass or more, and preferably 3 parts by mass or more with respect to 100 parts by mass of the rubber component, from the viewpoint of more reliably improving the peel resistance of the inner tube. More preferred.
  • the filler contains carbon black as an essential component.
  • the content of the carbon black is not particularly limited, but is less than 120 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of further improving the peel resistance of the inner tube without lowering the productivity. It is preferably 110 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 100 parts by mass or less. Further, the content of the carbon black is preferably 60 parts by mass or more, and 70 parts by mass or more with respect to 100 parts by mass of the rubber component, from the viewpoint of more reliably enhancing the peel resistance of the inner tube. Is preferable.
  • the type of carbon black is not particularly limited.
  • grade carbon blacks such as FEF, GPF, SRF, HAF, ISAF, SAF and the like can be used.
  • the carbon black preferably contains at least one carbon black selected from FEF, GPF and SRF, and more preferably contains at least FEF carbon black. This is because the inner tube peeling resistance can be improved more reliably.
  • the carbon black is FEF carbon black, the content thereof is preferably 70 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the rubber component.
  • the carbon black content of the FEF is 70 parts by mass or more with respect to 100 parts by mass of the rubber component, the inner tube peeling resistance and strength can be more reliably increased, and 100 parts by mass of the rubber component can be used.
  • 90 parts by mass or less it is possible to suppress deterioration of productivity and low heat generation.
  • silica and carbon black for example, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, and hydroxide. It can contain an inorganic filler such as magnesium, magnesium oxide, titanium oxide, potassium titanate, barium sulfate and the like.
  • the rubber composition for an inner hose tube of the present invention contains, in addition to the above-mentioned rubber component and filler, a vulcanization accelerator other than D) thiazole-based, which is 3.0 parts by mass or less with respect to 100 parts by mass of the rubber component.
  • a vulcanization accelerator other than the thiazole-based vulcanization accelerator as the vulcanization accelerator, it becomes possible to simultaneously vulcanize the rubber and bond the metal, and the adhesive performance between the rubber and the metal is enhanced. , The peel resistance of the inner tube can be improved.
  • a thiazole-based vulcanization accelerator When a thiazole-based vulcanization accelerator is contained as the vulcanization accelerator, it is difficult to simultaneously vulcanize rubber and bond with a metal, and sufficient inner tube peeling resistance cannot be obtained.
  • the rubber composition containing a thiazole-based vulcanization accelerator shall be excluded from the rubber composition. That is, the rubber composition of the present invention does not contain a thiazole-based vulcanization accelerator.
  • the vulcanization accelerator other than D) thiazole-based for example, sulfenamide-based, thiuram-based, dithiocarbamate-based, xanthogenate-based, guanidine-based, thiourea-based, aldehyde-ammonia-based, aldehyde- Examples thereof include amine-based vulcanization accelerators.
  • the vulcanization accelerator other than D) thiazole-based is a sulfenamide-based vulcanization accelerator. This is because the vulcanization reaction can be delayed and the rubber vulcanization and the metal are effectively bonded, so that more excellent inner tube peeling resistance can be realized.
  • the sulfenamide-based sulfide accelerating agent is not particularly limited, but for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CZ) and Nt-butyl-2-benzothiazolylsulfen.
  • N-methyl-Nt-butylbenzothiazole-2-sulfenamide BMBS
  • N-ethyl-Nt-butylbenzothiazole-2-sulfenamide BEBS
  • N-methyl-N-isoamylbenzothiazole- 2-Sulfenamide N-ethyl-N-isoamylbenzothiazole-2-sulfenamide, Nn-propyl-N-isoamylbenzothiazole-2-sulfenamide, Nn-butyl-N-isoamylbenzo Thiazol-2-sulfenamide, N-methyl-N-tert-amylbenzothiazole-2-sulfenamide, N-ethyl-
  • the sulfenamide-based vulcanization accelerators are N-cyclohexyl-2-benzothiazolyl sulfenamide (CZ) and Nt- from the viewpoint of achieving better inner tube peel resistance. It is preferable to use at least one of butyl-2-benzothiazolylsulfenamide (NS).
  • the content of the vulcanization accelerator other than D) thiazole-based is 3.0 parts by mass or less with respect to 100 parts by mass of the rubber component. If the content of the vulcanization accelerator other than D) thiazole-based exceeds 3.0 parts by mass with respect to 100 parts by mass of the rubber component, the progress rate of vulcanization becomes too fast, so that the inner tube is sufficiently resistant to peeling. You may not be able to get sex. From the same viewpoint, the content of the vulcanization accelerator other than D) thiazole-based is preferably 2.9 parts by mass or less, and 2.5 parts by mass or less with respect to 100 parts by mass of the rubber component. Is preferable.
  • the content of the vulcanization accelerator other than D) thiazole-based is 100 mass of rubber component from the viewpoint of more reliably realizing the bond between the vulcanization of rubber and the metal and obtaining more excellent inner tube peeling resistance. It is preferably 1.3 parts by mass or more, more preferably 2.0 parts by mass or more, and further preferably 2.1 parts by mass or more.
  • the rubber composition for an inner hose tube of the present invention may contain a cobalt compound as an optional component.
  • a cobalt compound By containing the cobalt compound, improvement in peel resistance of the inner tube can be expected.
  • the content of the cobalt compound needs to be 0.1% by mass or less with respect to the entire rubber composition for the inner hose pipe in terms of the amount of cobalt. It is preferably 05% by mass or less, and particularly preferably 0% (not contained).
  • the cobalt compound is a compound containing cobalt, and examples thereof include cobalt metal, cobalt oxide, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt phosphate, cobalt chromate, and cobalt organic acid. ..
  • the rubber composition for an inner hose pipe of the present invention appropriately contains a rubber component as an essential component, a filler and a vulcanization accelerator, and a component (other components) other than a cobalt compound as an optional component. Can be done.
  • Such other components include, for example, bismaleimide compounds, sulfur, vulcanization retarders, vulcanization accelerators, antioxidants, thermoplastics, petroleum resins, waxes, antioxidants, oils, lubricants, UV absorbers. , Dispersant, compatibilizer, co-crosslinking agent, homogenizing agent and the like.
  • the rubber composition for an inner hose tube of the present invention may contain a bismaleimide compound as another component.
  • the bismaleimide compound include a bismaleimide compound represented by the following general formula (I).
  • A represents a divalent aromatic group having 6 to 18 carbon atoms or a divalent alkyl aromatic group having 7 to 24 carbon atoms, and x and y are respectively. Independently represents an integer from 0 to 3. Further, in the bismaleimide compound represented by the above general formula (I), x or y is an integer of 0 to 3, but when it is 4 or more, the molecular weight becomes too large and the compounding amount is increased. It is inconvenient because the desired effect of improving the inner tube peelability cannot be obtained.
  • bismaleimide compound represented by the above general formula (I) include, for example, N, N'-1,2-phenylenedimaleimide, N, N'-1,3-phenylenedimaleimide, and the like.
  • N, N'-1,4-phenylenedimoleimide, N, N'-(4,4'-diphenylmethane) bismaleimide, 2,2-bis [4- (4-maleimide phenoxy) phenyl] propane, bis (3) -Ethyl-5-methyl-4-maleimidephenyl] methane and the like can be preferably mentioned.
  • These bismaleimide compounds may be blended in one or more kinds.
  • N, N'-1,2-phenylenedi maleimide, N, N'-1,3-phenylenedi maleimide or N, N'-1,4-phenylenedi maleimide is used. It is preferable, and it is more preferable to contain at least N, N'-(4,4'-diphenylmethane) bismaleimide.
  • the content of the bismaleimide compound in the rubber composition for an inner hose tube of the present invention is preferably 1 part by mass or more with respect to 100 parts by mass of the rubber component. This is because the content of the bismaleimide compound is 0.5% by mass or more with respect to 100 parts by mass of the rubber component, so that the adhesive strength of the rubber composition can be enhanced and the inner tube peelability can be further enhanced. From the same viewpoint, the content of the bismaleimide compound is more preferably 1 part by mass or more with respect to 100 parts by mass of the rubber component. Further, from the viewpoint of more reliably suppressing the decrease in the inner tube peelability due to excessive curing, the content of the bismaleimide compound is preferably 5 parts by mass or less with respect to 100 parts by mass of the rubber component. It is more preferably less than the mass part.
  • the rubber composition for an inner hose tube of the present invention usually contains sulfur as a vulcanizing agent.
  • the content thereof is not particularly limited, but is preferably 0.3 to 10 parts by mass, more preferably 1.0 to 7.0 parts by mass with respect to 100 parts by mass of the rubber component. It is more preferably 2.0 to 5.0 parts by mass.
  • sulfur content is 0.3 parts by mass or more with respect to 100 parts by mass of the rubber component, vulcanization can be sufficiently performed, and 10 parts by mass or less with respect to 100 parts by mass of the rubber component. , It is possible to suppress the deterioration of the aging performance of rubber.
  • the rubber composition for an inner tube of the present invention preferably further contains a vulcanization retarder as an essential component from the viewpoint of achieving better inner tube peel resistance.
  • a vulcanization retarder as an essential component from the viewpoint of achieving better inner tube peel resistance.
  • the content of the vulcanization retarder is not particularly limited.
  • the content of the vulcanization retarder is 1.5 mass by mass with respect to 100 parts by mass of the rubber component.
  • the content is preferably parts or less, and more preferably 1.3 parts by mass or less.
  • each of the above-mentioned components can be obtained by kneading with a Banbury mixer, a kneader or the like.
  • the laminate of the present invention is characterized by comprising a layer made of a vulcanized product of the rubber composition for an inner hose tube of the present invention described above, and a brass-plated wire.
  • the rubber composition for the inner hose pipe is as described above. Further, the conditions for vulcanizing the rubber composition for the inner hose tube are not particularly limited and can be adjusted according to the required performance. For example, a layer made of the vulcanized product can be obtained by performing a vulcanization treatment at 100 to 200 ° C. for 10 to 100 minutes.
  • the brass-plated wire constituting the laminated body of the present invention is not particularly limited and can be appropriately selected according to the required performance. Further, in the laminated body of the present invention, the brass-plated wire can be knitted into layers. When the laminate of the present invention is used for a hose, the layer made of the braided brass-plated wire constitutes a reinforcing layer.
  • the method of knitting the brass-plated wire is not particularly limited, and can be appropriately selected depending on the use of the laminated body. For example, it can be knitted into a spiral shape or a blade shape.
  • the laminated body of the present invention it is also possible to knit the brass-plated wire in combination with organic fibers.
  • organic fiber aramid fiber, polyester fiber, polyarylate fiber, nylon fiber, vinylon fiber, polyethylene terephthalate fiber, polyethylene naphthalate fiber, ultrahigh molecular weight polyethylene fiber, carbon-based fiber and the like can be used.
  • the hose of the present invention is characterized by having a laminate of the present invention arranged on the inner side in the radial direction of the hose and an outer skin rubber layer arranged on the outermost side in the radial direction of the hose.
  • a rubber inner surface rubber layer 2 inner tube rubber filled with hydraulic oil, a reinforcing layer 3 for withstanding the pressure of the hydraulic oil, and reinforcement thereof.
  • the hydraulic hose 1 can be formed by sequentially laminating an outer surface rubber layer 4 (cover rubber) that prevents the layer 3 and the inner surface rubber layer 2 from being damaged.
  • the vulcanized product of the rubber composition for the inner pipe of the hose constitutes the inner surface rubber layer 2
  • the brass-plated wire constitutes the reinforcing layer 3.
  • the hydraulic hose 1 When the hydraulic hose 1 is manufactured, it can be manufactured by the method shown below.
  • the rubber composition for an inner tube of the hose of the present invention is extruded on the outside of a core body (mandrel) having a diameter similar to the inner diameter of the hose to coat the mandrel to form an inner rubber layer (inner tube rubber) 2.
  • an inner rubber layer inner tube rubber
  • a predetermined number of brass-plated wires are knitted on the outside of the inner surface rubber layer 2 formed in the inner pipe extrusion step, and the reinforcing layer 3 is laminated (knitting step), and the outer cover of the hose is on the outside of the reinforcing layer 3.
  • the rubber composition to be used is extruded to form an outer surface rubber layer (outer rubber) 4 (outer cover extrusion step). Further, the outside of the outer surface rubber layer 4 formed in the outer cover extrusion step is coated with a resin (resin mold coating step), and this is vulcanized under normal conditions (vulcanization step). After vulcanization, the coating resin is peeled off (resin mold peeling step) and the mandrel is removed (mandrel extraction step), so that the hydraulic hose 1 having a reinforcing layer 3 between the inner tube rubber 2 and the outer cover rubber 4 Will be.
  • a resin resin
  • vulcanization step After vulcanization, the coating resin is peeled off (resin mold peeling step) and the mandrel is removed (mandrel extraction step), so that the hydraulic hose 1 having a reinforcing layer 3 between the inner tube rubber 2 and the outer cover rubber 4 Will be.
  • the structure of the hydraulic hose 1 may be a three-layer structure in which the inner tube rubber 2, the reinforcing layer 3 and the outer cover rubber 4 are sequentially laminated from the inside as described above, and especially when strength or the like is required.
  • the reinforcing layer may be two layers, and an intermediate layer (intermediate rubber) may be arranged between the reinforcing layers of the two layers to form a five-layer structure, and these structures are appropriately used according to the required characteristics of the hose and the like. Just set it.
  • the intermediate rubber examples include ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene ternary copolymer rubber (EPDM), acrylic rubber (ACM), chloroprene rubber (CR), and chlorosulfonated polyethylene rubber.
  • EPM ethylene-propylene copolymer rubber
  • EPDM ethylene-propylene-diene ternary copolymer rubber
  • ACM acrylic rubber
  • CR chloroprene rubber
  • chlorosulfonated polyethylene rubber examples include ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene ternary copolymer rubber (EPDM), acrylic rubber (ACM), chloroprene rubber (CR), and chlorosulfonated polyethylene rubber.
  • Hydrin rubber styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), isobutylene-isoprene copo
  • the intermediate rubber does not impair the object of the present invention by using known rubber compounding chemicals and rubber fillers generally used in the rubber industry in consideration of material strength, durability, extrusion moldability and the like.
  • examples of such compounding chemicals and fillers include inorganic fillers such as carbon black, silica and calcium carbonate; process oils, plasticizers and softeners; vulcanizers such as sulfur; addition of zinc oxide and stearic acid.
  • Vulcanization aid such as dibenzothiazyl disulfide
  • Vulcanization accelerator such as dibenzothiazyl disulfide
  • Anti-aging agent such as N-cyclohexyl-2-benzothiazyl-sulfurenamide, N-oxydiethylene-benzothiazyl-sulfurphenamide
  • Antioxidant Anti-sulfur deterioration Additives such as agents; etc.
  • One of these compounding chemicals and fillers may be used alone, or two or more thereof may be used in combination.
  • the outer cover rubber may be made of, for example, a layer made of a thermoplastic resin or the like, or may be made of the various rubbers, in the same manner as those used for conventional hydraulic hoses.
  • the present invention will be described in more detail with reference to examples, but these examples are for the purpose of exemplifying the present invention and do not limit the present invention in any way.
  • the blending amount means parts by mass unless otherwise specified.
  • Examples 1-41 According to the formulations shown in Tables 1 and 2, kneading was performed using a normal Banbury mixer to prepare each sample of the rubber composition for the hose inner tube. The content of each component in Tables 1 and 2 is shown by the amount (parts by mass) with respect to 100 parts by mass of the rubber component.
  • Mooney Viscosity The rubber composition for the inner hose tube of each sample was measured for Mooney viscosity in accordance with JIS K 630-1 (2001) "Mooney Viscosity, Mooney Scorch Time". The measurement results of the measured Mooney viscosity are shown in Tables 1 and 2. The smaller the value, the smaller the unvulcanized viscosity, and the larger the value, the harder it is. The range between 65 and 110 is acceptable in the production process. The range from 65 to 93 indicates that the productivity is particularly good.
  • the obtained test sample was subjected to a pull-out test by a method according to ASTM D2229, and the force required for pull-out (pull-out force (N)) was measured.
  • the force required for pull-out (pull-out force (N)) was measured.
  • the wire pulling force the larger the value, the larger the adhesive force between the rubber and the wire, and the better the inner tube peeling resistance.
  • Noxeller NS-P N- (cyclohexylthio) phthalimide, manufactured by Kawaguchi Chemical Industry Co., Ltd.
  • Anscoach CTP N, N'-m-phenylene bismaleimide (N, N'-1,3-phenylenedi maleimide), manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • BMI-3000H N- (cyclohexylthio) phthalimide
  • the present invention it is possible to provide a rubber composition for a hose inner tube that can realize excellent inner tube peeling resistance and productivity. Further, according to the present invention, it is possible to provide a laminate and a hose having excellent inner tube peeling resistance and productivity.

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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)

Abstract

La présente invention vise à fournir une composition de caoutchouc qui est destinée à des tubes internes de tuyau et qui est capable d'obtenir une excellente productivité et une excellente résistance au détachement de tube interne, même lorsque la quantité de composé de cobalt contenue est nulle ou faible.　La présente invention concerne par conséquent une composition de caoutchouc pour tubes internes de tuyau caractérisée en ce qu'elle contient, pour 100 parties en masse d'un composant de caoutchouc, A) 20 parties en masse ou moins d'un caoutchouc de butadiène, B) 80 parties en masse ou plus d'un caoutchouc acrylonitrile butadiène, C) moins de 10 parties en masse de silice, et D) 3,0 parties en masse ou moins d'un accélérateur de vulcanisation non à base de thiazole en tant que composants essentiels, et contenant un composé de cobalt en tant que composant facultatif. La présente invention est caractérisée en ce que la quantité contenue du composé de cobalt est de 0,1 % en masse ou moins en termes de teneur en cobalt, par rapport à la quantité totale de la composition de caoutchouc pour des tubes internes de tuyau, et en ce que pas d'accélérateur de vulcanisation à base de thiazole n'est contenu.
PCT/JP2021/040445 2020-11-27 2021-11-02 Composition de caoutchouc pour tubes internes de tuyau, et tuyau WO2022113671A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002361627A (ja) * 2001-06-08 2002-12-18 Yokohama Rubber Co Ltd:The 未加硫ゴム組成物の製造方法および未加硫ゴム組成物
JP2003160695A (ja) * 2001-11-27 2003-06-03 Jsr Corp 難燃性ゴム組成物及びゴム製品
JP2004250696A (ja) * 2003-01-29 2004-09-09 Yokohama Rubber Co Ltd:The ホース層間ゴム用ゴム組成物およびホース
JP2007291295A (ja) * 2006-04-27 2007-11-08 Toyo Tire & Rubber Co Ltd 耐水性ニトリルゴム組成物
JP2008168522A (ja) * 2007-01-12 2008-07-24 Bridgestone Corp ゴムマンドレル
JP2012102288A (ja) * 2010-11-12 2012-05-31 Yokohama Rubber Co Ltd:The スタッドレスタイヤトレッド用ゴム組成物
WO2014136668A1 (fr) * 2013-03-05 2014-09-12 ダイキン工業株式会社 Composition de caoutchouc acrylonitrile butadiène, article moulé de caoutchouc acrylonitrile butadiène et leur procédé de fabrication
JP2017002175A (ja) * 2015-06-09 2017-01-05 株式会社ブリヂストン ホース用ゴム組成物及びホース
JP2017019984A (ja) * 2015-07-13 2017-01-26 横浜ゴム株式会社 ホース用ゴム組成物及びホース
WO2020074751A1 (fr) * 2018-10-08 2020-04-16 L. Brüggemann Gmbh & Co. Kg Composition de caoutchouc ayant des propriétés de durcissement et d'adhérence améliorées, procédé pour sa préparation, et produits en caoutchouc modifiés fabriqués à partir de celle-ci

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002361627A (ja) * 2001-06-08 2002-12-18 Yokohama Rubber Co Ltd:The 未加硫ゴム組成物の製造方法および未加硫ゴム組成物
JP2003160695A (ja) * 2001-11-27 2003-06-03 Jsr Corp 難燃性ゴム組成物及びゴム製品
JP2004250696A (ja) * 2003-01-29 2004-09-09 Yokohama Rubber Co Ltd:The ホース層間ゴム用ゴム組成物およびホース
JP2007291295A (ja) * 2006-04-27 2007-11-08 Toyo Tire & Rubber Co Ltd 耐水性ニトリルゴム組成物
JP2008168522A (ja) * 2007-01-12 2008-07-24 Bridgestone Corp ゴムマンドレル
JP2012102288A (ja) * 2010-11-12 2012-05-31 Yokohama Rubber Co Ltd:The スタッドレスタイヤトレッド用ゴム組成物
WO2014136668A1 (fr) * 2013-03-05 2014-09-12 ダイキン工業株式会社 Composition de caoutchouc acrylonitrile butadiène, article moulé de caoutchouc acrylonitrile butadiène et leur procédé de fabrication
JP2017002175A (ja) * 2015-06-09 2017-01-05 株式会社ブリヂストン ホース用ゴム組成物及びホース
JP2017019984A (ja) * 2015-07-13 2017-01-26 横浜ゴム株式会社 ホース用ゴム組成物及びホース
WO2020074751A1 (fr) * 2018-10-08 2020-04-16 L. Brüggemann Gmbh & Co. Kg Composition de caoutchouc ayant des propriétés de durcissement et d'adhérence améliorées, procédé pour sa préparation, et produits en caoutchouc modifiés fabriqués à partir de celle-ci

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