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WO2018155722A1 - Courroie de transmission - Google Patents

Courroie de transmission Download PDF

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Publication number
WO2018155722A1
WO2018155722A1 PCT/JP2018/007368 JP2018007368W WO2018155722A1 WO 2018155722 A1 WO2018155722 A1 WO 2018155722A1 JP 2018007368 W JP2018007368 W JP 2018007368W WO 2018155722 A1 WO2018155722 A1 WO 2018155722A1
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WO
WIPO (PCT)
Prior art keywords
parts
mass
rubber
transmission belt
belt
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PCT/JP2018/007368
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English (en)
Japanese (ja)
Inventor
利樹 尾崎
日根野　順文
幹夫 景山
Original Assignee
三ツ星ベルト株式会社
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Priority claimed from JP2018012694A external-priority patent/JP6616852B2/ja
Application filed by 三ツ星ベルト株式会社 filed Critical 三ツ星ベルト株式会社
Priority to EP18758077.4A priority Critical patent/EP3587859B1/fr
Priority to RU2019126799A priority patent/RU2719606C9/ru
Priority to US16/489,143 priority patent/US20190390047A1/en
Priority to CA3053901A priority patent/CA3053901C/fr
Publication of WO2018155722A1 publication Critical patent/WO2018155722A1/fr

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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
    • 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
    • C08K3/18—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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/14—Peroxides
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • 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
    • F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G5/00—V-belts, i.e. belts of tapered cross-section
    • F16G5/04—V-belts, i.e. belts of tapered cross-section made of rubber
    • 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
    • F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G5/00—V-belts, i.e. belts of tapered cross-section
    • F16G5/04—V-belts, i.e. belts of tapered cross-section made of rubber
    • F16G5/06—V-belts, i.e. belts of tapered cross-section made of rubber with reinforcement bonded by the rubber
    • F16G5/08—V-belts, i.e. belts of tapered cross-section made of rubber with reinforcement bonded by the rubber with textile reinforcement
    • 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
    • F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G5/00—V-belts, i.e. belts of tapered cross-section
    • F16G5/20—V-belts, i.e. belts of tapered cross-section with a contact surface of special shape, e.g. toothed
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • 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
    • F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G5/00—V-belts, i.e. belts of tapered cross-section
    • F16G5/04—V-belts, i.e. belts of tapered cross-section made of rubber
    • F16G5/06—V-belts, i.e. belts of tapered cross-section made of rubber with reinforcement bonded by the rubber

Definitions

  • the present invention relates to a transmission belt including a cured product of a rubber composition including an ethylene- ⁇ -olefin elastomer capable of realizing high hardness and high modulus.
  • V-belts and V-ribbed belts are commonly used for driving automotive engine accessories, toothed belts for driving OHC (overhead camshaft), and low-edge cogged V-belts for driving CVT (continuously variable transmission).
  • OHC overhead camshaft
  • CVT continuously variable transmission
  • the low-edge cogged V-belt used for driving CVTs such as snowmobiles has a wide temperature range from a low temperature to a high temperature because it is exposed to the heat generated by the engine while driving at a low temperature while starting.
  • a rubber composition that can withstand the region is required.
  • high adhesiveness for suppressing separation between the rubber composition and a fiber member such as a core wire or a reinforcing cloth, and bending fatigue resistance that can be applied to a small-diameter pulley are required for compactness.
  • a high wear resistance that can withstand wear due to contact with the pulley and a high side pressure resistance that can withstand the side pressure from the pulley are also required.
  • a toothed belt is also required to have a small belt width for compactness, and in order to cope with this, high hardness and high modulus of tooth rubber are required.
  • the use of ethylene- ⁇ -olefin elastomers as elastomers constituting rubber compositions is increasing.
  • Ethylene- ⁇ -olefin elastomers have high heat resistance and weather resistance because they do not have an unsaturated bond in the main chain. Furthermore, since the ethylene- ⁇ -olefin elastomer does not have a polar group, it can be highly filled with reinforcing agents such as short fibers and carbon black, and it is relatively easy to achieve high hardness and high modulus. It also has features. However, when an ethylene- ⁇ -olefin elastomer is highly filled with a reinforcing agent, it has the following drawbacks. That is, when a large amount of carbon black is added, the heat generated due to the bending of the belt increases, and the durability tends to decrease. Further, when a large amount of short fibers is added, poor dispersion is likely to occur, and cracks are likely to occur. For this reason, various formulations have been studied that increase the hardness and modulus while relatively reducing the amount of reinforcing agent.
  • Patent Document 1 100 parts by weight of an ethylene- ⁇ -olefin elastomer having an ethylene content of 55 to 78% by weight and a metal salt 1 to 30 of an ⁇ , ⁇ -unsaturated organic acid are disclosed.
  • a belt (synchronous belt, V-belt, V-ribbed belt) comprising a crosslinked product obtained by crosslinking an elastomer composition containing parts by weight and a reinforcing agent of 0 to 250 parts by weight (preferably 25 to 100 parts by weight) with a free radical donor.
  • the reinforcing agent carbon black, calcium carbonate, talc, clay and hydrous silica are described.
  • Patent Document 2 discloses that ⁇ -ethylene-propylene-diene terpolymer (EPDM) having an ethylene content of 50 to 65% by weight and a diene content of less than 10% by weight is ⁇ , ⁇ -unsaturated carboxylic acid metal salt 32 to 100 parts by weight and filler 0 to 30 parts by weight, and a power transmission belt (V-ribbed belt, toothed belt) including a peroxide-crosslinked crosslinked product is disclosed. .
  • the filler a white filler such as silicate; aluminum, calcium or magnesium oxide or carbonate is described.
  • a composition containing 40 to 60 parts by weight of zinc diacrylate, 10 parts by weight of white filler, 25 parts by weight of carbon black, and 5 parts by weight of dicumyl hydroperoxide is prepared with respect to 100 parts by weight of EPDM.
  • Patent Document 3 100 parts by mass of an ethylene- ⁇ -olefin elastomer containing 5% by mass to less than 40% by mass of ethylene propylene diene monomer rubber having an ethylene content of 66 to 85% by mass,
  • a power transmission belt comprising a crosslinked product obtained by crosslinking a composition containing 32 to 100 parts by mass of an ⁇ , ⁇ -unsaturated carboxylic acid metal salt with an organic peroxide is disclosed.
  • transmission belts flat transmission belts, friction transmission belts such as V-belts and V-ribbed belts, and meshing transmission belts such as toothed belts are described.
  • Patent Documents 1 to 3 the ethylene content of the ethylene- ⁇ -olefin elastomer is regulated within a certain range, and the addition amount of the organic acid metal salt is adjusted to obtain a rubber composition having the required performance. Can be estimated.
  • these compositions only adjust the balance between the crystallinity due to the ethylene component and the crosslinking with the organic acid metal salt, and even if a belt is formed, cold resistance, heat resistance, adhesiveness, and bending resistance Various requirements required for a transmission belt such as fatigue and wear resistance cannot be satisfied at the same time.
  • Patent Document 4 describes 20 to 40 parts by weight of an organic acid metal salt monomer per 100 parts by weight of a rubber component composed of an ethylene- ⁇ -olefin elastomer and a hydrogenated nitrile rubber. And a high load transmission belt (cogged V belt, hybrid V belt) comprising a crosslinked product obtained by crosslinking a composition containing 5 to 35 parts by weight of short fibers with peroxide.
  • Patent Document 4 hydrogenated nitrile rubber is blended with ethylene- ⁇ -olefin elastomer to improve crack resistance, but the properties of ethylene- ⁇ -olefin elastomer such as cold resistance are reduced. The result is a moderate or good performance. Moreover, since it becomes an inhomogeneous composition of the sea-island structure, there is a concern about separation at the time of deterioration over time.
  • Patent Document 5 a composition containing chloroprene rubber as a main rubber and containing a metal oxide, an organic peroxide, and an ⁇ , ⁇ -unsaturated fatty acid metal salt is disclosed.
  • a power transmission belt (a V-ribbed belt, a V-belt, a cogged V-belt, a flat belt) including a crosslinked product crosslinked with an oxide is disclosed.
  • zinc oxide, magnesium oxide, and calcium oxide are exemplified as metal oxides, and the function of the metal oxide is described as a function as a cross-linking agent and a function as an acid acceptor (corrosion prevention of mold). ing.
  • a V-ribbed belt using a composition containing 5 to 20 parts by mass of aluminum acrylate, 4 parts by mass of magnesium oxide, 5 parts by mass of zinc oxide and an organic peroxide with respect to 100 parts by mass of chloroprene rubber is disclosed. Has been.
  • Patent Document 5 has a problem of improving adhesive wear of a transmission belt containing chloroprene rubber, and does not describe a problem of an ethylene- ⁇ -olefin elastomer having a structure and characteristics that are significantly different from those of chloroprene rubber. Furthermore, the cold resistance, heat resistance, and weather resistance of chloroprene rubber are not as good as those of ethylene- ⁇ -olefin elastomers, and are insufficient in the recent severe use environment such as low edge cogged V-belts.
  • the performance required for the recent transmission belt cannot be sufficiently satisfied.
  • the hardness and modulus of rubber, the adhesiveness, the bending fatigue resistance required for the belt, and the durability in a wide temperature range are in a trade-off relationship, It was difficult to achieve both.
  • the object of the present invention is to improve the hardness and modulus of a cured product of a rubber composition mainly composed of an ethylene- ⁇ -olefin elastomer without impairing cold resistance, heat resistance, adhesion, bending fatigue resistance, and wear resistance.
  • An object of the present invention is to provide a transmission belt including a cured product of a rubber composition that can be enhanced.
  • the present inventors have found that an ethylene- ⁇ -olefin elastomer, an ⁇ , ⁇ -unsaturated carboxylic acid metal salt, magnesium oxide, an organic peroxide, and an inorganic filler.
  • magnesium oxide an organic peroxide
  • an inorganic filler by adjusting the ratio of the magnesium oxide, transmission with ethylene- ⁇ -olefin elastomer as the main component without impairing cold resistance, heat resistance, adhesion, bending fatigue resistance, and wear resistance.
  • the present inventors have found that the hardness and modulus of the cured product of the rubber composition for belts can be increased.
  • the transmission belt of the present invention is a rubber containing a rubber component containing an ethylene- ⁇ -olefin elastomer, an ⁇ , ⁇ -unsaturated carboxylic acid metal salt, magnesium oxide, an organic peroxide, and an inorganic filler.
  • a transmission belt comprising a cured product of the composition, wherein the proportion of the magnesium oxide is 2 to 20 parts by mass with respect to 100 parts by mass of the rubber component, and the ⁇ , ⁇ -unsaturated carboxylic acid metal salt 100 It is 5 mass parts or more with respect to a mass part.
  • the proportion of the ⁇ , ⁇ -unsaturated carboxylic acid metal salt may be about 5 to 40 parts by mass with respect to 100 parts by mass of the rubber component.
  • the ratio of the organic peroxide may be about 2 to 6 parts by mass with respect to 100 parts by mass of the rubber component.
  • the proportion of magnesium oxide may be about 5 to 300 parts by mass with respect to 100 parts by mass of the ⁇ , ⁇ -unsaturated carboxylic acid metal salt.
  • the rubber component may contain 80% by mass or more of an ethylene- ⁇ -olefin elastomer.
  • the ethylene- ⁇ -olefin elastomer may contain 80% by mass or more of an ethylene-propylene-diene terpolymer.
  • the ⁇ , ⁇ -unsaturated carboxylic acid metal salt may be at least one selected from zinc methacrylate and zinc acrylate.
  • the inorganic filler may contain carbon black.
  • the proportion of the inorganic filler may be about 40 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
  • the inorganic filler may further contain silica.
  • the rubber composition may further contain zinc oxide.
  • the cured product of the rubber composition may have a cured product having a rubber hardness (JIS-A) of about 91 to 98 degrees.
  • the rubber composition may further contain short fibers.
  • the proportion of the short fibers may be about 20 to 40 parts by mass with respect to 100 parts by mass of the rubber component.
  • the short fiber may be an aramid short fiber.
  • the rubber composition may include short fibers, and the cured product of the rubber composition may have a bending stress of about 8 to 15 MPa in a direction perpendicular to the orientation direction of the short fibers.
  • the power transmission belt of the present invention may be a low edge cogged V belt used for CVT driving.
  • the “direction orthogonal to the orientation direction” does not have to be a completely orthogonal direction, and may be a direction in the range of the orthogonal direction ⁇ 5 °.
  • the ratio of the magnesium oxide is adjusted in a combination of an ethylene- ⁇ -olefin elastomer, an ⁇ , ⁇ -unsaturated carboxylic acid metal salt, magnesium oxide, an organic peroxide, and an inorganic filler. Therefore, the hardness and modulus of the cured product of the rubber composition mainly composed of ethylene- ⁇ -olefin elastomer can be increased without impairing cold resistance, heat resistance, adhesion, bending fatigue resistance, and wear resistance. Can do.
  • a transmission belt such as a low-edge cogged V-belt or a toothed belt, which is required to increase transmission power and to make the layout compact, and particularly to a low-edge cogged V-belt used for CTV driving.
  • FIG. 1 is a schematic perspective view showing an example of a transmission belt (low edge cogged V belt) of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the transmission belt of FIG. 1 cut in the belt longitudinal direction.
  • FIG. 3 is a schematic diagram for explaining a method of measuring the bending stress of the transmission belt obtained in the example.
  • FIG. 4 is a schematic diagram for explaining a durability running test of the transmission belt obtained in the example.
  • FIG. 5 is a schematic perspective view of a double cogged V-belt manufactured in the example.
  • the transmission belt of the present invention is a rubber composition containing a rubber component containing an ethylene- ⁇ -olefin elastomer, an ⁇ , ⁇ -unsaturated carboxylic acid metal salt, magnesium oxide, an organic peroxide, and an inorganic filler. It is sufficient if the cured product is included.
  • the rubber component preferably contains an ethylene- ⁇ -olefin elastomer from the viewpoint of excellent cold resistance, heat resistance, and weather resistance.
  • ethylene- ⁇ -olefin elastomer examples include ethylene- ⁇ -olefin rubber and ethylene- ⁇ -olefin-diene rubber.
  • Examples of the ⁇ -olefin constituting the elastomer include linear ⁇ -C 3-12 olefins such as propylene, butene, pentene, methylpentene, hexene and octene. These ⁇ -olefins can be used alone or in combination of two or more. Of these ⁇ -olefins, ⁇ -C 3-4 olefins (particularly propylene) such as propylene are preferred.
  • Examples of the diene monomer constituting the elastomer usually include non-conjugated diene monomers such as dicyclopentadiene, methylene norbornene, ethylidene norbornene, 1,4-hexadiene, and cyclooctadiene. These diene monomers can be used alone or in combination of two or more. Of these diene monomers, ethylidene norbornene and 1,4-hexadiene (particularly ethylidene norbornene) are preferred.
  • ethylene- ⁇ -olefin elastomers include, for example, ethylene- ⁇ -olefin rubber [ethylene-propylene rubber (EPM), ethylene-butene rubber (EBM), ethylene-octene rubber (EOM), etc.], ethylene- ⁇ -olefin. -Diene rubber [ethylene-propylene-diene terpolymer (EPDM)] and the like. These ethylene- ⁇ -olefin elastomers can be used alone or in combination of two or more.
  • EPM ethylene-propylene rubber
  • EBM ethylene-butene rubber
  • EOM ethylene-octene rubber
  • EPDM ethylene-propylene-diene terpolymer
  • ethylene- ⁇ -olefin-dienes such as ethylene- ⁇ -C 3-4 olefin-diene terpolymer rubbers are excellent because of their excellent cold resistance, heat resistance, and weather resistance.
  • Ternary copolymer rubber is preferred, and EPDM is particularly preferred. Therefore, the proportion of EPDM may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more (particularly 95% by mass) with respect to the total ethylene- ⁇ -olefin elastomer. It may be mass% (EPDM only).
  • the proportion of the diene monomer can be selected from the range of about 1 to 15% by mass, for example, 1.5 to 12% by mass, preferably 2 to 10%, based on the whole elastomer. It may be about mass% (especially 2.5 to 5 mass%).
  • the iodine value of the ethylene- ⁇ -olefin elastomer containing a diene monomer may be, for example, about 3 to 40, preferably about 5 to 30, and more preferably about 10 to 20. If the iodine value is too small, vulcanization of the rubber composition will be insufficient and wear and adhesion will easily occur. Conversely, if the iodine value is too large, the scorch of the rubber composition will become short and difficult to handle and heat resistance Tend to decrease.
  • ethylene- ⁇ -olefin elastomer in addition to the ethylene- ⁇ -olefin elastomer, other rubber components such as diene rubber [natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, styrene Butadiene rubber (SBR), vinylpyridine-styrene-butadiene copolymer rubber, acrylonitrile butadiene rubber (nitrile rubber); hydrogenated nitrile rubber (including mixed polymer of hydrogenated nitrile rubber and unsaturated carboxylic acid metal salt), etc.
  • diene rubber natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, styrene Butadiene rubber (SBR), vinylpyridine-styrene-butadiene copolymer rubber, acrylonitrile butadiene rubber (nitrile rubber); hydrogenated nitrile rubber (including mixed polymer of hydrogenated nitrile rubber and unsaturated
  • olefin rubbers polyoctenylene rubber, ethylene-vinyl acetate copolymer rubber, chlorosulfonated polyethylene rubber, alkylated chlorosulfonated polyethylene rubber, etc.
  • epichlorohydrin rubber acrylic Rubber, silicone rubber, cormorant Tangomu
  • acrylic Rubber silicone rubber, cormorant Tangomu
  • fluorine rubber may contain a such as fluorine rubber.
  • the ratio of the ethylene- ⁇ -olefin elastomer may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more (particularly 95% by mass or more), and 100% by mass. It may be mass% (rubber component is ethylene- ⁇ -olefin elastomer only). If the proportion of the ethylene- ⁇ -olefin elastomer is too small, the cold resistance and heat resistance may be lowered.
  • the ⁇ , ⁇ -unsaturated carboxylic acid metal salt may be a compound in which an unsaturated carboxylic acid having one or more carboxyl groups and a metal are ionically bonded.
  • unsaturated carboxylic acid include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid. These unsaturated carboxylic acids can be used alone or in combination of two or more. Of these unsaturated carboxylic acids, unsaturated monocarboxylic acids such as (meth) acrylic acid are preferred.
  • Examples of the metal include Group 2 metals (magnesium, calcium, etc.), Group 4 metals (titanium, zirconium, etc.), Group 8 metals (iron, etc.), Group 10 metals (nickel, etc.), Examples include Group metals (such as copper), Group 12 metals (such as zinc), Group 13 metals (such as aluminum), and Group 14 metals (such as lead). These metals can be used alone or in combination of two or more. Of these metals, polyvalent metals, for example, divalent metals such as magnesium, calcium and zinc, and trivalent metals such as aluminum (especially divalent metals such as zinc) are preferable.
  • bifunctional monocarboxylic acid divalent metal salts having two radical polymerizable groups in one molecule for example, zinc (meth) acrylate such as zinc methacrylate [zinc di (meth) acrylate or bis (Meth) acrylic acid zinc], magnesium (meth) acrylates such as magnesium methacrylate, and trifunctional monocarboxylic acid trivalent metal salts having three radical polymerizable groups in one molecule, such as (meth) acrylic Preferred are aluminum acrylate [aluminum tri (meth) acrylate], more preferably zinc (meth) acrylate and / or aluminum acrylate, selected from zinc (meth) acrylate (ie, zinc methacrylate and zinc acrylate). At least one) is particularly preferred. Furthermore, a bifunctional monocarboxylic acid divalent metal salt (particularly zinc methacrylate) is preferable from the viewpoint of excellent balance of various properties.
  • the proportion of the ⁇ , ⁇ -unsaturated carboxylic acid metal salt is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 8 to 35 parts by weight (particularly 10 to 30 parts by weight) based on 100 parts by weight of the rubber component. Part) degree. If the proportion of the ⁇ , ⁇ -unsaturated carboxylic acid metal salt is too small, the hardness and modulus of the cured product of the rubber composition may be reduced. On the other hand, if the proportion is too large, the adhesion and bending fatigue resistance will be reduced. There is a risk of doing.
  • Magneium oxide In the present invention, by combining magnesium oxide at a predetermined ratio with the ⁇ , ⁇ -unsaturated carboxylic acid metal salt, cold resistance, heat resistance, adhesiveness, and bending fatigue resistance of the cured product of the rubber composition The hardness and modulus can be improved while maintaining the wear resistance.
  • the proportion of magnesium oxide is 2 to 20 parts by weight, preferably 3 to 18 parts by weight, more preferably 5 to 15 parts by weight (particularly 8 to 13 parts by weight) with respect to 100 parts by weight of the rubber component. May be.
  • the proportion of magnesium oxide is 5 parts by mass or more (eg, 5 to 300 parts by mass) with respect to 100 parts by mass of the ⁇ , ⁇ -unsaturated carboxylic acid metal salt, for example, 5 to 250 parts by mass (eg, 5 to 200 parts by mass). Part), preferably 10 to 150 parts by weight, more preferably about 15 to 100 parts by weight (particularly 20 to 80 parts by weight). If the proportion of magnesium oxide is too small, the hardness and modulus of the cured product of the rubber composition may be decreased. Conversely, if the proportion is too large, adhesiveness and bending fatigue resistance may be decreased.
  • organic peroxide organic peroxides usually used for crosslinking of rubber and resin, for example, diacyl peroxide, peroxy ester, dialkyl peroxide (for example, dicumyl peroxide, t-butyl cumyl peroxide) are used. Oxide, 1,1-di-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, 1,3-bis (t- Butylperoxy-isopropyl) benzene, di-t-butyl peroxide, etc.). These organic peroxides can be used alone or in combination of two or more. Further, the organic peroxide is preferably a peroxide having a decomposition temperature of about 150 to 250 ° C. (for example, 175 to 225 ° C.) for obtaining a half-life of 1 minute by thermal decomposition.
  • the proportion of the organic peroxide is, for example, about 1 to 10 parts by weight, preferably 2 to 8 parts by weight, more preferably 2 to 6 parts by weight (eg 3 to 6 parts by weight) with respect to 100 parts by weight of the rubber component. It may be.
  • the cured product of the rubber composition has cold resistance, heat resistance, adhesion, and bending resistance. Wear resistance, hardness, and modulus can be improved while maintaining fatigue.
  • inorganic fillers examples include carbonaceous materials (carbon black, graphite, etc.), metal compounds or synthetic ceramics [metal oxides such as calcium oxide, barium oxide, iron oxide, copper oxide, titanium oxide, and aluminum oxide. (Metal oxides other than magnesium oxide and zinc oxide), metal silicates such as calcium silicate and aluminum silicate, metal carbides such as silicon carbide and tungsten carbide, metal nitride such as titanium nitride, aluminum nitride and boron nitride , Metal carbonates such as magnesium carbonate and calcium carbonate, metal sulfates such as calcium sulfate and barium sulfate], mineral materials (zeolite, diatomaceous earth, calcined diatomaceous earth, activated clay, alumina, silica, talc, mica, kaolin , Sericite, bentonite, montmorillo Ito, smectite, such as clay), and the like.
  • metal compounds or synthetic ceramics metal oxides
  • carbon black and / or silica are preferable, and it is particularly preferable that at least carbon black is included in the cured product of the rubber composition from the viewpoint of improving the hardness, modulus, and wear resistance.
  • carbon black examples include SAF, ISAF, HAF, FEF, GPF, and HMF. These carbon blacks can be used alone or in combination of two or more. Among these, FEF is preferable because the balance between the reinforcing effect and the dispersibility is good and the heat generated when the belt is bent is small.
  • the average particle size of carbon black can be selected from the range of, for example, about 5 to 200 nm, and is, for example, about 10 to 150 nm, preferably 15 to 100 nm, and more preferably 20 to 80 nm (particularly 30 to 50 nm). If the average particle size of the carbon black is too small, uniform dispersion may be difficult, and if it is too large, the hardness, modulus, and wear resistance may be reduced.
  • the inorganic filler containing carbon black is combined with silica from the viewpoint that adhesion can be improved in addition to hardness, modulus and wear resistance.
  • Silica is a fine bulky white powder formed of silicic acid and / or silicate, and has a plurality of silanol groups on its surface, so it can be chemically bonded to the rubber component.
  • Silica includes dry silica, wet silica, surface-treated silica, and the like. Silica can also be classified into, for example, dry process white carbon, wet process white carbon, colloidal silica, precipitated silica, and the like according to the classification in the production method. These silicas can be used alone or in combination of two or more. Of these, wet-type white carbon containing hydrous silicic acid as a main component is preferable because it has many surface silanol groups and a strong chemical bonding force with a rubber component.
  • the average particle diameter of silica is, for example, about 1 to 1000 nm, preferably 3 to 300 nm, more preferably 5 to 100 nm (particularly 10 to 50 nm). If the particle size of the silica is too large, the cured product of the rubber composition may have reduced mechanical properties. If it is too small, it may be difficult to uniformly disperse.
  • Silica may be non-porous or porous, but the nitrogen adsorption specific surface area by the BET method is, for example, 50 to 400 m 2 / g, preferably 70 to 350 m 2 / g, more preferably 100. It may be about ⁇ 300 m 2 / g (especially 150 to 250 m 2 / g). If the specific surface area is too large, it may be difficult to uniformly disperse, and if the specific surface area is too small, the mechanical properties of the rubber layer may be deteriorated.
  • the proportion of the inorganic filler can be selected from the range of about 10 to 150 parts by mass with respect to 100 parts by mass of the rubber component, for example, 40 to 100 parts by mass, preferably 50 to 80 parts by mass, and more preferably 60 to 70 parts by mass. About a part. If the proportion of the inorganic filler is too small, the hardness, modulus and wear resistance of the cured product of the rubber composition may be reduced, and conversely if too large, the bending fatigue resistance may be reduced.
  • the total ratio of carbon black and silica may be 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass with respect to the entire inorganic filler. % Or more (especially 80% by mass or more), or 90% by mass or more (particularly 100% by mass).
  • the rubber composition may further contain zinc oxide.
  • zinc oxide as the metal oxide in addition to the magnesium oxide, hardness and modulus can be improved and the balance of various properties can be improved in the cured product of the rubber composition.
  • the proportion of zinc oxide is, for example, about 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight (particularly 3 to 8 parts by weight) with respect to 100 parts by weight of the rubber component. It may be.
  • the proportion of zinc oxide is, for example, about 10 to 1000 parts by weight, preferably 20 to 500 parts by weight, more preferably 30 to 200 parts by weight (particularly 50 to 100 parts by weight) with respect to 100 parts by weight of magnesium oxide. Also good. If the proportion of zinc oxide is too small or too large, the balance of various properties may be lowered.
  • the rubber composition may further contain short fibers.
  • short fibers include polyolefin fibers (polyethylene fibers, polypropylene fibers, etc.), polyamide fibers (polyamide 6 fibers, polyamide 66 fibers, polyamide 46 fibers, aramid fibers, etc.), polyalkylene arylate fibers (polyethylene terephthalate (PET)).
  • Fibers poly C 2-4 alkylene C 6-14 arylate fibers such as polyethylene naphthalate (PEN) fibers, etc.], vinylon fibers, polyvinyl alcohol fibers, synthetic fibers such as polyparaphenylene benzobisoxazole (PBO) fibers; Natural fibers such as cotton, hemp and wool; inorganic fibers such as carbon fibers are widely used.
  • These short fibers can be used alone or in combination of two or more.
  • synthetic fibers and natural fibers, especially synthetic fibers are rigid and have high strength and modulus, and are at least easy to protrude from the surface of the compressed rubber layer.
  • Aramid short fibers are preferred. Aramid short fibers also have high wear resistance. Aramid fibers are commercially available, for example, under the trade names “Conex”, “Nomex”, “Kevlar”, “Technola”, “Twaron”, and the like.
  • the average fiber diameter of the short fibers is, for example, about 1 to 100 ⁇ m, preferably 3 to 50 ⁇ m, more preferably about 5 to 30 ⁇ m (particularly 10 to 20 ⁇ m). If the average fiber diameter is too large, the cured product of the rubber composition may have reduced mechanical properties. If it is too small, it may be difficult to disperse uniformly.
  • the average length of the short fibers may be, for example, about 1 to 20 mm, preferably about 1.2 to 15 mm (for example, 1.5 to 10 mm), and more preferably about 2 to 5 mm (especially 2.5 to 4 mm). If the average length of the short fibers is too short, when the cured product of the rubber composition is used for the belt, the mechanical properties (for example, the modulus) in the direction of preparation may not be sufficiently improved. In addition, the dispersibility of the short fibers in the rubber composition may be reduced, and the bending fatigue resistance may be reduced.
  • At least the short fibers are preferably subjected to an adhesion treatment (or surface treatment).
  • an adhesion treatment or surface treatment
  • various adhesion treatments for example, treatment solutions containing an initial condensate of phenols and formalin (such as a prepolymer of a novolak or resol type phenol resin), treatment solutions containing a rubber component (or latex).
  • treatment solutions containing an initial condensate of phenols and formalin such as a prepolymer of a novolak or resol type phenol resin
  • treatment solutions containing a rubber component or latex
  • Treatment with a treatment liquid containing the initial condensate and a rubber component (latex), a silane coupling agent, an epoxy compound (epoxy resin, etc.), a treatment liquid containing a reactive compound (adhesive compound) such as an isocyanate compound, etc. be able to.
  • the short fibers are treated with a treatment solution containing the precondensate and a rubber component (latex), particularly at least a resorcin-formalin-latex (RFL) solution.
  • a treatment solution containing the precondensate and a rubber component (latex), particularly at least a resorcin-formalin-latex (RFL) solution may be used in combination.
  • short fibers may be pre-treated with a conventional adhesive component such as an epoxy compound (epoxy resin or the like) or a reactive compound (adhesive compound) such as an isocyanate compound. After processing, you may process with RFL liquid.
  • the proportion of short fibers is, for example, about 5 to 100 parts by weight, preferably 10 to 50 parts by weight, more preferably 20 to 40 parts by weight (especially 25 to 35 parts by weight) with respect to 100 parts by weight of the rubber component. May be. If the proportion of short fibers is too small, the mechanical properties of the cured product of the rubber composition may be reduced. Conversely, if the proportion is too large, it may be difficult to uniformly disperse and the bending fatigue resistance may be reduced. There are (other additives)
  • the rubber composition may be prepared by using conventional additives, vulcanization aids, vulcanization accelerators, vulcanization retarders, and softeners (oils such as paraffinic oil, naphthenic oil, and process oil) as necessary.
  • Processing agents or processing aids stearic acid, stearic acid metal salts, wax, paraffin, fatty acid amide, etc.
  • anti-aging agents antioxidants, thermal anti-aging agents, anti-bending cracking agents, anti-ozone degradation agents, etc.
  • Colorants tackifiers
  • plasticizers coupling agents (such as silane coupling agents), stabilizers (such as UV absorbers and heat stabilizers), lubricants, flame retardants, antistatic agents, etc. Good.
  • coupling agents such as silane coupling agents
  • stabilizers such as UV absorbers and heat stabilizers
  • lubricants flame retardants, antistatic agents, etc. Good.
  • the total proportion of other additives may be about 1 to 100 parts by weight, preferably about 5 to 50 parts by weight, and more preferably about 10 to 20 parts by weight with respect to 100 parts by weight of the rubber component.
  • the ratio of the softening agent is 1 to 20 parts by mass (especially 5 to 15 parts by mass)
  • the ratio of the processing (auxiliary) agent is 0.1 to 5 parts by mass (particularly 0.5).
  • the proportion of the antioxidant may be about 0.5 to 20 parts by mass (particularly 1 to 10 parts by mass).
  • the cured product of the rubber composition has a large rubber hardness and modulus.
  • the rubber hardness (JIS-A) of the cured product of the rubber composition is, for example, 90 to 100 degrees, preferably 91 to 98 degrees (eg 93 to 97 degrees), more preferably 95 to 98 degrees (particularly 96). (About 97 degrees).
  • rubber hardness (JIS-A) is measured in accordance with JIS K6253 (2012) for a cured product obtained by press vulcanization at a temperature of 170 ° C. and a pressure of 2.0 MPa for 20 minutes. In detail, it measures by the method as described in the below-mentioned Example.
  • the cured product of the rubber composition has a bending stress of, for example, 8 to 15 MPa, preferably 10 to 15 MPa, more preferably 12 to 14.5 MPa (particularly 13 to 14.5 MPa) in a direction perpendicular to the orientation direction of the short fibers. It may be a degree. In the present specification and claims, the bending stress is measured by the method described in Examples described later.
  • the “direction orthogonal to the orientation direction” is not limited to a direction orthogonal to the orientation direction, but may be a direction in a range of ⁇ 5 ° in the orthogonal direction. Therefore, the “direction orthogonal to the alignment direction” can also be referred to as a “direction substantially orthogonal to the alignment direction”.
  • the short fibers are usually oriented in a predetermined direction.
  • the compression rubber layer of the transmission belt is formed with the rubber composition, in order to suppress the compression deformation of the belt against the pressure from the pulley, the short fibers are embedded in the compression rubber layer oriented in the belt width direction. It is preferable.
  • the rubber composition is used as a cured product vulcanized by a method according to the application.
  • the vulcanization temperature may be, for example, about 120 to 200 ° C. (especially 150 to 180 ° C.).
  • Examples of the transmission belt of the present invention include friction transmission belts such as flat belts, V-belts, V-ribbed belts, wrapped V-belts, low-edge V-belts, low-edge cogged V-belts, resin block belts, and meshing transmission belts such as toothed belts. Etc. These power transmission belts only need to contain the rubber composition, but usually the belt body (particularly the compression rubber layer and / or the stretch rubber layer) is formed of a cured product of the rubber composition.
  • transmission belts such as cogged belts and toothed belts, which are required to increase transmission power and make the layout compact, are preferable, and cogged belts are particularly preferable.
  • the cogged belt of the present invention includes an adhesive rubber layer in contact with at least a part of a core wire extending in the longitudinal direction of the belt, an extended rubber layer formed on one surface of the adhesive rubber layer, and the other surface of the adhesive rubber layer.
  • a compression rubber layer having a plurality of convex portions (cog portions) formed at predetermined intervals along the longitudinal direction of the belt and frictionally engaging with the pulleys on the side surfaces As long as it has.
  • Such a cogged belt includes a cogged belt in which the cogged portion is formed only on the compressed rubber layer, and a double cogged belt in which a similar cogged portion is formed on the outer peripheral surface of the stretched rubber layer in addition to the compressed rubber layer.
  • the cogged belt is preferably a V-belt whose side surface of the compression rubber layer is in contact with the pulley (in particular, a transmission belt used in a transmission in which the transmission ratio changes steplessly while the belt is running).
  • Examples of the cogged V belt include a low edge cogged V belt in which a cog is formed on the inner peripheral side of the low edge belt, and a low edge double cogged V belt in which cogs are formed on both the inner peripheral side and the outer peripheral side of the low edge belt. Can be mentioned. Of these, the low-edge cogged V-belt used for CTV driving is particularly preferable.
  • FIG. 1 is a schematic perspective view showing an example of a transmission belt (low edge cogged V belt) of the present invention
  • FIG. 2 is a schematic sectional view of the transmission belt of FIG. 1 cut in the longitudinal direction of the belt.
  • the low edge cogged V-belt 1 has a plurality of cogs 1a formed at predetermined intervals along the longitudinal direction of the belt (A direction in the figure) on the inner peripheral surface of the belt body.
  • the cross-sectional shape in the longitudinal direction of the cog 1a is substantially semicircular (curved or corrugated), and the cross-sectional shape in the direction (width direction or B direction in the figure) perpendicular to the longitudinal direction. Is trapezoidal. That is, each cog 1a protrudes from the cog bottom 1b in a cross section in the A direction in a substantially semicircular shape in the belt thickness direction.
  • the low-edge cogged V-belt 1 has a laminated structure, and the reinforcing cloth 2, the stretch rubber layer 3, and the adhesive rubber layer 4 from the belt outer peripheral side toward the inner peripheral side (side where the cog portion 1a is formed).
  • the compressed rubber layer 5 and the reinforcing cloth 6 are sequentially laminated.
  • the cross-sectional shape in the belt width direction is a trapezoidal shape in which the belt width decreases from the belt outer peripheral side toward the inner peripheral side.
  • a core body 4a is embedded in the adhesive rubber layer 4, and the cog 1a is formed on the compressed rubber layer 5 by a cog-molding mold.
  • the height and pitch of the cog are the same as the conventional cogged V belt.
  • the height of the cog portion is about 50 to 95% (especially 60 to 80%) with respect to the thickness of the entire compressed rubber layer, and the pitch of the cog portion (between the central portions of adjacent cog portions).
  • the distance) is about 50 to 250% (especially 80 to 200%) with respect to the height of the cog portion. The same applies to the case where a cog portion is formed in the stretched rubber layer.
  • the stretch rubber layer 3 and the compression rubber layer 5 are formed of a cured product of the rubber composition of the present invention.
  • the adhesive rubber layer, the core, and the reinforcing cloth a conventional adhesive rubber layer, core, and reinforcing cloth can be used.
  • the following adhesive rubber layer, core, and reinforcing cloth may be used.
  • the rubber composition for forming the adhesive rubber layer is a rubber component, a vulcanizing agent or a cross-linking agent (such as a sulfur-based vulcanizing agent such as sulfur) in the same manner as the vulcanized rubber composition of the compressed rubber layer and the stretch rubber.
  • a vulcanizing agent or a cross-linking agent such as a sulfur-based vulcanizing agent such as sulfur
  • Co-crosslinking agent or crosslinking aid such as maleimide crosslinking agent such as N, N'-m-phenylene dimaleimide), vulcanization accelerator (such as TMTD, DPTT, CBS), inorganic filler (such as carbon black, silica) , Softeners (oils such as paraffinic oils), processing agents or processing aids, anti-aging agents, adhesion improvers [resorcin-formaldehyde cocondensates, amino resins (condensates of nitrogen-containing cyclic compounds and formaldehyde, For example, melamine resins such as hexamethylol melamine, hexaalkoxymethyl melamine (hexamethoxymethyl melamine, hexabutoxymethyl melamine, etc.), methyl Urea resins such as roll urea, benzoguanamine resins such as methylol benzoguanamine resin), co-condensates thereof (such as resorcin-mel
  • the resorcin-formaldehyde cocondensate and amino resin may be an initial condensate (prepolymer) of a nitrogen-containing cyclic compound such as resorcin and / or melamine and formaldehyde.
  • the rubber component the same type or type of rubber as the rubber component of the rubber composition of the compressed rubber layer and the stretched rubber layer is often used. Further, the ratios of the vulcanizing agent or crosslinking agent, co-crosslinking agent or crosslinking aid, vulcanization accelerator, softening agent and anti-aging agent are the same ranges as the rubber composition of the compression rubber layer and the stretch rubber layer, respectively. You can choose from.
  • the proportion of the inorganic filler is 10 to 100 parts by weight, preferably 20 to 80 parts by weight, more preferably about 30 to 50 parts by weight with respect to 100 parts by weight of the rubber component. There may be.
  • the ratio of the adhesion improver is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 100 parts by weight of the rubber component. May be about 2 to 8 parts by mass.
  • the core wire (twisted cord) arranged at predetermined intervals in the belt width direction can be used.
  • the cores are arranged to extend in the longitudinal direction of the belt, and are usually arranged to extend in parallel at a predetermined pitch in parallel with the longitudinal direction of the belt.
  • the core wire only needs to be at least partially in contact with the adhesive rubber layer.
  • the adhesive rubber layer embeds the core wire, the core wire embeds between the adhesive rubber layer and the stretch rubber layer, and the adhesive rubber. Any form of embedding a core wire between the layer and the compressed rubber layer may be employed. Among these, the form in which the adhesive rubber layer embeds the core wire is preferable from the viewpoint that durability can be improved.
  • Examples of the fibers constituting the core wire include the same fibers as the short fibers.
  • these fibers from the viewpoint of high modulus, synthesis of polyester fibers (polyalkylene arylate fibers) mainly composed of C 2-4 alkylene arylates such as ethylene terephthalate and ethylene-2,6-naphthalate, aramid fibers, etc.
  • Inorganic fibers such as fibers and carbon fibers are widely used, and polyester fibers (polyethylene terephthalate fibers, polyethylene naphthalate fibers) and polyamide fibers are preferable.
  • the fiber may be a multifilament yarn.
  • the fineness of the multifilament yarn may be, for example, about 2200 to 13500 dtex (particularly 6600 to 11000 dtex).
  • the multifilament yarn may contain, for example, 100 to 5,000, preferably 500 to 4,000, more preferably about 1,000 to 3,000 monofilament yarns.
  • the core wire usually a twisted cord using multifilament yarn (for example, various twists, single twists, rung twists, etc.) can be used.
  • the average wire diameter (fiber diameter of the twisted cord) of the core wire may be, for example, 0.5 to 3 mm, preferably 0.6 to 2 mm, more preferably about 0.7 to 1.5 mm. Good.
  • the core wire may be subjected to adhesion treatment (or surface treatment) in the same manner as the short fibers of the compression rubber layer and the stretch rubber layer in order to improve the adhesion with the rubber component.
  • adhesion treatment or surface treatment
  • the core wire is preferably subjected to adhesion treatment with at least the RFL solution.
  • the reinforcing cloth is not limited to a form in which the reinforcing cloth is laminated on the surface of the compressed rubber layer.
  • the reinforcing cloth is applied to the surface of the stretched rubber layer (the surface opposite to the adhesive rubber layer). It may be laminated, or may be a form in which a reinforcing layer is embedded in a compressed rubber layer and / or a stretched rubber layer (for example, a form described in Japanese Patent Application Laid-Open No. 2010-230146).
  • the reinforcing cloth can be formed of, for example, a cloth material (preferably a woven cloth) such as a woven cloth, a wide angle sail cloth, a knitted cloth, and a non-woven cloth.
  • a cloth material preferably a woven cloth
  • the above-described adhesion treatment for example, treatment with an RFL solution (immersion treatment) Or the like, or after the adhesive rubber and the cloth material are laminated, they may be laminated on the surface of the compression rubber layer and / or the stretch rubber layer.
  • the method for producing the transmission belt of the present invention is not particularly limited, and a conventional method can be used.
  • a low-edge cogged V-belt for example, a laminated body composed of a reinforcing cloth (lower cloth) and a sheet for a compressed rubber layer (unvulcanized rubber sheet), and teeth and grooves are alternately arranged with the reinforcing cloth facing down.
  • both ends of the cog pad may be cut vertically from the top of the cog crest.
  • an inner mother mold formed of vulcanized rubber in which teeth and grooves are alternately arranged is placed on a cylindrical mold, and a cog pad is wound around the teeth and grooves so that a cog pad is wound.
  • the core wire (twisting cord) that forms the core body is joined Spinning in a spiral shape
  • a second adhesive rubber layer sheet (upper adhesive rubber: the same as the adhesive rubber layer sheet), a stretch rubber layer sheet (unvulcanized rubber sheet), a reinforcing cloth (upper cloth) ) May be sequentially wound to produce a molded body.
  • a jacket (jacket made of vulcanized rubber) is put on and the mold is placed in a vulcanizing can, and vulcanized at a temperature of about 120 to 200 ° C (especially 150 to 180 ° C) to prepare a belt sleeve.
  • a cutting process may be performed using a cutter or the like to form a compressed rubber layer by cutting so as to form a V-shaped cross section.
  • a conventional method for example, rubber between a pair of calendar rolls provided with a predetermined gap is used.
  • a method described in Japanese Patent Laid-Open No. 2003-14054 can be used. In this method, the unvulcanized sheet in which short fibers are oriented by such a method is placed and vulcanized so that the orientation direction of the short fibers is the width direction of the belt.
  • EPDM1 "EP93” manufactured by JSR Corporation, ethylene content 55 wt%, diene content 2.7 wt%
  • EPDM2 “EP24” manufactured by JSR Corporation, ethylene content 54% by weight, diene content 4.5% by weight
  • Para-type aramid short fiber Teijin Co., Ltd., Twaron cut yarn
  • Meta-type aramid short fiber Teijin Ltd., Cornex cut yarn Carbon black: “Cabot Japan Co., Ltd.”
  • N550 Silica: “Ultrasil VN3” manufactured by Evonik Degussa Japan, BET specific surface area of 175 m 2 / g Paraffin oil: “Diana Process Oil PW90” manufactured by Idemitsu Kosan Co., Ltd.
  • Anti-aging agent A “NOCRACK CD” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
  • Anti-aging agent B “NOCRACK MB” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
  • Anti-aging agent C “Nonflex OD3” manufactured by Seiko Chemical Co., Ltd.
  • Zinc oxide “Zinc oxide 2 types” manufactured by Sakai Chemical Industry Co., Ltd.
  • Magnesium oxide “Kyowa Mug 150” manufactured by Kyowa Chemical Industry Co., Ltd.
  • Stearic acid Tsubaki stearic acid manufactured by NOF Corporation Zinc methacrylate: Sanshin Chemical Industry Co., Ltd., “Sunester SK-30” Bismaleimide: Ouchi Shinsei Chemical Co., Ltd., “Barnock PM” Organic peroxide: NOF "P-40MB (K)” Titanium oxide: DuPont “R960” Resorcinol resin: “Penacolite Resin (B-18-S)” manufactured by INDSPEC Chemical Corporation Hexamethoxymethylolmelamine: “PP-1890S” manufactured by Power Plast Vulcanization accelerator A: “Noxeller TT” manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Vulcanization accelerator B “Noxeller CZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Vulcanization accelerator C “Noxeller DM” manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Sulfur Made by Bigen Chemical Co., Ltd.
  • Core wire Total fineness of two aramid fiber bundles with a fineness of 1,680 dtex, twisted together and twisted together, and twisted in the opposite direction to the twist 10,080 dtex plied cords
  • Reinforcement fabric Nylon canvas with a 2/2 twill weave (thickness 0.50 mm).
  • the front end portion of the pressing member 23 has a semicircular shape with a diameter of 10 mm, and the vulcanized rubber molded body 21 can be smoothly pressed by the front end portion. Further, at the time of pressing, a frictional force acts between the lower surface of the vulcanized rubber molded body 21 and the rolls 22a and 22b along with the compression deformation of the vulcanized rubber molded body 21, but the rolls 22a and 22b can be rotated. This reduces the influence of friction.
  • a state where the tip of the pressing member 23 is in contact with the upper surface of the vulcanized rubber molded body 21 and is not pressed is set as an initial position. From this state, the vulcanized rubber molded body is moved downward at a speed of 100 mm / min.
  • the upper surface of 21 was pressed, and the stress when the bending strain was 8% was measured as the bending stress.
  • the measurement temperature was 120 ° C. assuming the belt temperature during running.
  • the endurance running test was performed using a two-axis running tester including a driving (Dr.) pulley 32 having a diameter of 110 mm and a driven (Dn.) Pulley 33 having a diameter of 240 mm.
  • Dr. driving
  • Dn. driven
  • a low-edge cogged V-belt 31 was hung on each pulley, a drive pulley rotation speed of 6000 rpm and a load of 25 kW was applied, and the belt was run at an ambient temperature of 80 ° C. for 70 hours.
  • the side of the belt after running (the surface in contact with the pulley) was visually observed, and the presence or absence of delamination between the compressed rubber layer and the core wire was examined and the presence or absence of cracks in the lower cog valley was evaluated.
  • Examples 1 to 9 and Comparative Examples 1 to 7 [Properties of rubber composition of compressed rubber layer and stretched rubber layer] (Formation of rubber layer)
  • the rubber compositions in Table 1 (compressed rubber layer, stretched rubber layer) and Table 2 (adhesive rubber layer) were each kneaded using a known method such as a Banbury mixer, and the kneaded rubber was passed through a calender roll.
  • Rolled rubber sheets (compressed rubber layer sheet, stretch rubber layer sheet, adhesive rubber layer sheet) were prepared. The rubber hardness and bending stress were measured for the compressed rubber layer sheet. Table 3 shows the measurement results. Furthermore, the following belts were manufactured using these sheets.
  • the temperature is 170 ° C., time 40 minutes, and vulcanized at 0.9 MPa.
  • vulcanization conditions conditions similar to vulcanization of unvulcanized adhesive rubber layer sheets, compressed rubber layer sheets and stretched rubber layer sheets were selected. This sleeve was cut into a V shape by a cutter to finish a transmission belt. That is, a double cogged V belt having the structure shown in FIG. 5 was produced.
  • Comparative Example 1 (corresponding to Patent Document 3) not containing magnesium oxide and Comparative Example 2 containing only 1 part by mass of magnesium oxide with respect to 100 parts by mass of the rubber component, the rubber hardness is as low as 90 degrees. Peeling occurred. When the proportion of magnesium oxide is small, the rubber hardness does not increase, and stress is concentrated on the adhesion interface due to buckling deformation, which is considered to cause peeling. Further, Comparative Example 6 and Comparative Example 7 are examples in which the amount of zinc oxide was increased and titanium oxide was added in Comparative Example 1. In these examples, the hardness and bending stress were low as in Comparative Example 1, and peeling occurred in the durability running test.
  • Comparative Example 5 is an example in which zinc methacrylate was not included and bismaleimide was blended as a co-crosslinking agent, but in this case also, the rubber hardness was low and peeling occurred.
  • Comparative Example 3 is an example containing a large amount of magnesium oxide
  • Comparative Example 4 is an example containing a large amount of zinc methacrylate.
  • both examples although the rubber hardness and bending stress increased greatly, cracks occurred in the durability running test. This is presumably because the dispersion was poor due to too much magnesium oxide, or the rubber composition became stiff due to too much zinc methacrylate and the bending fatigue resistance decreased. It can be seen that magnesium oxide and the ⁇ , ⁇ -unsaturated carboxylic acid metal salt need to be blended in a well-balanced manner.
  • Examples 1 and 2 are examples in which the types of short fibers were changed, but the configuration of the present invention was equally effective for both para-aramid short fibers and meta-aramid short fibers. .
  • Example 3 is an example in which the amount of magnesium oxide is increased with respect to Example 1, but the hardness and bending stress are increased, and it can be seen that the effect is enhanced.
  • Example 4 is an example in which the amount of zinc methacrylate is increased with respect to Example 3
  • Example 7 is an example in which the amount of zinc methacrylate is increased with respect to Example 1.
  • the hardness and bending stress are remarkably high, and the effect is particularly high.
  • Example 5 is an example in which the amount of magnesium oxide was increased with respect to Example 3.
  • the hardness and bending stress were also significantly increased, and particularly good results were obtained.
  • Example 6 is an example in which a large amount of magnesium oxide was blended and the mass ratio of magnesium oxide to zinc methacrylate was 2.86, but the increase in hardness and bending stress was small. However, in the durability running test, peeling and cracking did not occur, and the performance had no problem in practical use.
  • Example 8 is an example in which a part of carbon black was replaced with silica as an inorganic filler from the formulation of Example 3, but the hardness and bending stress were slightly increased, and particularly good results were obtained. Silica also has a function of improving the adhesiveness, and it is expected that the resistance to peeling will increase even when running for a longer time.
  • Example 9 is an example in which the amount of organic peroxide was reduced from the formulation of Example 4, but compared with Example 4, hardness and bending stress were slightly reduced. However, even when the amount of the organic peroxide (crosslinking agent) is small, the hardness and bending stress are high, and even in the durability running test, peeling or cracking does not occur, and the performance has no practical problem.
  • the transmission belt of the present invention has various transmission belts (flat belt, V-belt, V-ribbed belt, wrapped V-belt, low-edge V-belt) that are required to have cold resistance, heat resistance, adhesion, bending fatigue resistance, wear resistance, and the like.
  • Friction power transmission belts such as low edge cogged V belts and resin block belts; meshing power transmission belts such as toothed belts).
  • the transmission belt of the present invention has high hardness and modulus, it can be preferably used as a transmission belt such as a cogged belt or a toothed belt, which is required to increase transmission power and to make the layout compact.
  • a low-edge cogged V-belt used as

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  • 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)
  • Textile Engineering (AREA)
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Abstract

Selon la présente invention, la dureté et le module d'un produit durci d'une composition de caoutchouc pour des courroies de transmission, ladite composition de caoutchouc étant principalement composée d'un élastomère d'éthylène-α-oléfine, sont améliorés sans détériorer la résistance au froid, la résistance à la chaleur, l'adhésivité, la résistance à la fatigue en flexion et la résistance à l'usure. Selon la présente invention, une courroie de transmission est formée à partir d'un produit durci d'une composition de caoutchouc qui contient un constituant de caoutchouc qui contient un élastomère d'éthylène-α-oléfine, un sel métallique d'acide carboxylique à insaturation α,β, un oxyde de magnésium, un peroxyde organique et une charge inorganique, et qui est ajusté de telle sorte que le rapport de l'oxyde de magnésium soit de 2 à 20 parties en masse par rapport à 100 parties en masse du constituant de caoutchouc, tout en étant supérieur ou égal à 5 parties en masse par rapport à 100 parties en masse du sel métallique d'acide carboxylique à insaturation α,β. Le rapport du sel métallique d'acide carboxylique à insaturation α,β peut être d'environ 5 à 40 parties en masse par rapport à 100 parties en masse du constituant de caoutchouc. Cette courroie de transmission est applicable en tant que courroie de transmission qui est utilisée pour un entraînement de transmission à variation continue, tel qu'une courroie trapézoïdale crantée à bord brut.
PCT/JP2018/007368 2017-02-27 2018-02-27 Courroie de transmission WO2018155722A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18758077.4A EP3587859B1 (fr) 2017-02-27 2018-02-27 Courroie de transmission
RU2019126799A RU2719606C9 (ru) 2017-02-27 2018-02-27 Приводной ремень
US16/489,143 US20190390047A1 (en) 2017-02-27 2018-02-27 Transmission Belt
CA3053901A CA3053901C (fr) 2017-02-27 2018-02-27 Courroie de transmission

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JP2017-035198 2017-02-27
JP2017035198 2017-02-27
JP2018-012694 2018-01-29
JP2018012694A JP6616852B2 (ja) 2017-02-27 2018-01-29 伝動ベルト

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US10716912B2 (en) 2015-03-31 2020-07-21 Fisher & Paykel Healthcare Limited User interface and system for supplying gases to an airway
US11324908B2 (en) 2016-08-11 2022-05-10 Fisher & Paykel Healthcare Limited Collapsible conduit, patient interface and headgear connector
WO2023054413A1 (fr) * 2021-09-29 2023-04-06 三ツ星ベルト株式会社 Courroie crantée et procédé pour sa fabrication
JP7255006B1 (ja) 2021-09-29 2023-04-10 三ツ星ベルト株式会社 歯付ベルトおよびその製造方法

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IT202200006695A1 (it) * 2022-04-05 2023-10-05 Dayco Europe Srl Cinghia cvt

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US10716912B2 (en) 2015-03-31 2020-07-21 Fisher & Paykel Healthcare Limited User interface and system for supplying gases to an airway
US11904097B2 (en) 2015-03-31 2024-02-20 Fisher & Paykel Healthcare Limited User interface and system for supplying gases to an airway
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US11324908B2 (en) 2016-08-11 2022-05-10 Fisher & Paykel Healthcare Limited Collapsible conduit, patient interface and headgear connector
WO2023054413A1 (fr) * 2021-09-29 2023-04-06 三ツ星ベルト株式会社 Courroie crantée et procédé pour sa fabrication
JP7255006B1 (ja) 2021-09-29 2023-04-10 三ツ星ベルト株式会社 歯付ベルトおよびその製造方法
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TWI864449B (zh) * 2021-09-29 2024-12-01 日商三星皮帶股份有限公司 齒型皮帶及其製造方法

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