WO2016038854A1 - Composite caoutchouc-fibre - Google Patents

Composite caoutchouc-fibre Download PDF

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Publication number
WO2016038854A1
WO2016038854A1 PCT/JP2015/004461 JP2015004461W WO2016038854A1 WO 2016038854 A1 WO2016038854 A1 WO 2016038854A1 JP 2015004461 W JP2015004461 W JP 2015004461W WO 2016038854 A1 WO2016038854 A1 WO 2016038854A1
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WO
WIPO (PCT)
Prior art keywords
rubber
mass
layer
fiber composite
vulcanization accelerator
Prior art date
Application number
PCT/JP2015/004461
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English (en)
Japanese (ja)
Inventor
尚 松田
勝起 木村
Original Assignee
バンドー化学株式会社
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Application filed by バンドー化学株式会社 filed Critical バンドー化学株式会社
Priority to JP2016521374A priority Critical patent/JP6159883B2/ja
Publication of WO2016038854A1 publication Critical patent/WO2016038854A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D29/00—Producing belts or bands
    • 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
    • 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
    • F16G1/00—Driving-belts
    • F16G1/06—Driving-belts made of rubber
    • F16G1/08—Driving-belts made of rubber with reinforcement bonded by the rubber

Definitions

  • the present invention relates to a rubber fiber composite such as a transmission belt and a manufacturing method thereof.
  • Patent Document 1 discloses that an adhesive rubber layer of a transmission belt is EPDM, 100 parts by mass of sulfur as a crosslinking agent, 1 part by mass of sulfur, 1 part by mass of a thiuram vulcanization accelerator, and thiazole. It is disclosed that a rubber composition containing 1 part by mass of a system vulcanization accelerator is formed.
  • the present invention is a rubber fiber composite including a structure in which a rubber member and a fiber member subjected to an adhesion treatment are combined, and the fiber member subjected to the adhesion treatment mainly includes an ethylene- ⁇ -olefin elastomer.
  • the rubber component is mixed with a vulcanization accelerator having a thiocarbonyl group and is in contact with the rubber composition crosslinked with an organic peroxide.
  • the present invention relates to a method for producing a rubber fiber composite including a structure in which a rubber member and a fiber member subjected to an adhesion treatment are combined, wherein the fiber member subjected to the adhesion treatment is treated with an ethylene- ⁇ -olefin elastomer.
  • a non-crosslinked rubber composition in which a vulcanization accelerator having a thiocarbonyl group and an organic peroxide are blended with a rubber component mainly composed of the above, and the uncrosslinked rubber composition is crosslinked with the organic peroxide.
  • FIG. 3 is a perspective view of a V-ribbed belt according to Embodiment 1.
  • FIG. It is sectional drawing which shows the interface structure of a back reinforcement cloth and an adhesive rubber layer. It is sectional drawing which shows the structure of the reinforcement cloth adhesive layer of a 1st example. It is sectional drawing which shows the structure of the reinforcement cloth adhesive layer of the 2nd example. It is sectional drawing which shows the structure of the reinforcement cloth adhesive layer of the 3rd example. It is sectional drawing which shows the structure of the reinforcement cloth adhesive layer of the 4th example. It is sectional drawing which shows the interface structure of a core wire and an adhesive rubber layer. It is sectional drawing which shows the structure of the core wire contact bonding layer of a 1st example.
  • FIG. 5 is a first explanatory view showing a method for manufacturing the V-ribbed belt according to the first embodiment.
  • FIG. 6 is a second explanatory view showing the method for manufacturing the V-ribbed belt according to the first embodiment.
  • FIG. 6 is a third explanatory view showing the method for manufacturing the V-ribbed belt according to the first embodiment.
  • FIG. 6 is a fourth explanatory view showing the method for manufacturing the V-ribbed belt according to the first embodiment.
  • FIG. 9 is a fifth explanatory view showing the method for manufacturing the V-ribbed belt according to the first embodiment. It is a perspective view of the low edge type V belt concerning other embodiments. It is a perspective view of the wrapped V belt concerning other embodiments. It is a perspective view of the flat belt which concerns on other embodiment. It is a perspective view of the toothed belt which concerns on other embodiment. It is a perspective view of the test piece for adhesion tests. It is a figure which shows the pulley layout of a belt test traveling machine.
  • FIG. 1 shows a V-ribbed belt B (rubber fiber composite) according to the first embodiment.
  • the V-ribbed belt B according to the first embodiment is an endless transmission belt used in, for example, a belt transmission device for driving auxiliary equipment provided in an engine room of an automobile.
  • the V-ribbed belt B according to Embodiment 1 has, for example, a belt length of 700 to 3000 mm, a belt width of 10 to 36 mm, and a belt thickness of 4.0 to 5.0 mm.
  • the V-ribbed belt B includes a rubber-made V-ribbed belt body 10 configured as a double layer of an adhesive rubber layer 11 on the belt outer peripheral side and a compression rubber layer 12 that forms a pulley contact portion on the belt inner peripheral side. I have.
  • a back reinforcing cloth 13 is attached to the belt outer peripheral side of the adhesive rubber layer 11 in the V-ribbed belt main body 10.
  • a core wire 14 is embedded in an intermediate portion in the thickness direction of the adhesive rubber layer 11 so as to form a spiral having a pitch in the belt width direction.
  • the adhesive rubber layer 11 is formed in a band shape having a horizontally long cross section and has a thickness of, for example, 1.0 to 2.5 mm.
  • the adhesive rubber layer 11 is formed of a rubber composition in which a rubber component is crosslinked by heating and pressurizing an uncrosslinked rubber composition in which various rubber compounds are blended with a rubber component.
  • the rubber component of the rubber composition forming the adhesive rubber layer 11 is mainly composed of an ethylene- ⁇ -olefin elastomer.
  • the content of the ethylene- ⁇ -olefin elastomer in the rubber component is more than 50% by mass, preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass.
  • the rubber component may contain, for example, chloroprene rubber or hydrogenated nitrile rubber in addition to the ethylene- ⁇ -olefin elastomer.
  • ethylene- ⁇ -olefin elastomers examples include ethylene-propylene-diene terpolymer (hereinafter referred to as “EPDM”), ethylene-propylene copolymer (EPM), ethylene-butene copolymer (EDM), and ethylene-octene copolymer (EOM). Etc. Of these, EPDM is preferred.
  • the rubber component may contain only one kind of ethylene- ⁇ -olefin elastomer among the above or may contain two or more kinds of ethylene- ⁇ -olefin elastomers.
  • the ethylene content of the ethylene- ⁇ -olefin elastomer is preferably 48% by mass or more, more preferably 50% by mass or more, and preferably 65% by mass or less, more preferably 60% by mass or less.
  • examples of the diene component include ethylidene nobornene, dicyclopentadiene, 1,4-hexadiene, and the like. Of these, ethylidene nobornene is preferred.
  • the diene component content is preferably 1.5% by mass or more, more preferably 2.5% by mass or more, further preferably 3.0% by mass or more, and preferably 13% by mass or less, more preferably 11% by mass. % Or less, more preferably 10% by mass or less.
  • the Mooney viscosity of the ethylene- ⁇ -olefin elastomer is preferably 10 ML 1 + 4 (125 ° C.) or more, more preferably 15 ML 1 + 4 (125 ° C.) or more, and preferably 100 ML 1 + 4 (125 ° C.) or less, more preferably 80 ML. 1 + 4 (125 ° C.) or less.
  • Mooney viscosity is measured based on JISK6300.
  • the rubber composition forming the adhesive rubber layer 11 is crosslinked with an organic peroxide. That is, an organic peroxide is blended in the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 as a crosslinking agent.
  • organic peroxide examples include dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like. .
  • the organic peroxide either one of the above may be blended or two or more may be blended.
  • the content of the organic peroxide in the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.7% by mass. Further, it is preferably 6.5% by mass or less, more preferably 5.5% by mass or less, and further preferably 5.0% by mass or less.
  • the rubber composition forming the adhesive rubber layer 11 may be cross-linked with sulfur. That is, the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 may contain sulfur as a crosslinking agent in addition to the organic peroxide.
  • the sulfur content in the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.4% by mass or more. Moreover, it is preferably 1.7% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.2% by mass or less.
  • the ratio of sulfur content to organic peroxide content in the uncrosslinked rubber composition before formation of the adhesive rubber layer 11 is preferably 0.1 or more. More preferably, it is 0.2 or more, More preferably, it is 0.25 or more, Preferably it is 2.0 or less, More preferably, it is 1.5 or less, More preferably, it is 1.3 or less.
  • the sulfur content in the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 is preferably larger than the content of the organic peroxide.
  • the rubber composition forming the adhesive rubber layer 11 is blended with a vulcanization accelerator having a thiocarbonyl group.
  • vulcanization accelerator having a thiocarbonyl group examples include thiourea vulcanization accelerators such as N, N′-diphenylthiourea, trimethylthiourea (TMU), and N, N′-diethylthiourea (DEU); tetramethylthiuram Thiuram such as disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TBTD), tetrakis (2-ethylhexyl) thiuram disulfide, tetramethylthiuram monosulfide (TMTM), dipentamethylenethiuram tetrasulfide (DPTT) Vulcanization accelerators: piperidinium pentamethylenedithiocarbamate (PPDC), zinc dimethyldithiocarbamate (ZnMDC), zinc diethyldithiocarbamate (ZnEDC), di
  • the vulcanization accelerator having a thiocarbonyl group preferably includes a thiuram vulcanization accelerator or a dithiocarbamate vulcanization accelerator, and more preferably includes a thiuram vulcanization accelerator.
  • One of the vulcanization accelerators having a thiocarbonyl group may be blended, or two or more may be blended.
  • the blending amount of the vulcanization accelerator having a thiocarbonyl group in the rubber composition forming the adhesive rubber layer 11 is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass with respect to 100 parts by mass of the rubber component. Part or more, more preferably 0.8 part by weight or more, preferably 3.0 part by weight or less, more preferably 2.5 parts by weight or less, and further preferably 2.0 parts by weight or less.
  • the content of the vulcanization accelerator having a thiocarbonyl group in the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably.
  • the content of the vulcanization accelerator having a thiocarbonyl group in the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 is preferably not more than the content of the organic peroxide, and more preferably less than that. .
  • Ratio of content of vulcanization accelerator having thiocarbonyl group to content of organic peroxide in uncrosslinked rubber composition before formation of adhesive rubber layer 11 is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and preferably 1.0 or less, more preferably 0.8. Hereinafter, more preferably 0.7 or less.
  • the ratio of the content of the vulcanization accelerator having a thiocarbonyl group to the content of sulfur in the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and preferably 6.0 or less, more preferably Is 3.0 or less, more preferably 2.0 or less.
  • the content of the vulcanization accelerator having a thiocarbonyl group in the uncrosslinked rubber composition before the formation of the adhesive rubber layer 11 is preferably not more than the sulfur content, and more preferably less.
  • the rubber composition forming the adhesive rubber layer 11 may contain only a vulcanization accelerator having a thiocarbonyl group, or may contain other vulcanization accelerators in combination.
  • vulcanization accelerators other than those having a thiocarbonyl group include aldehyde-ammonia vulcanization accelerators, aldehyde-amine vulcanization accelerators, thiourea vulcanization accelerators, and guanidine vulcanization accelerators.
  • Examples of other rubber blends blended in the rubber composition forming the adhesive rubber layer 11 include, for example, reinforcing materials such as carbon black, softeners, vulcanization accelerating aids, processing aids, anti-aging agents, and co-crosslinking. Agents and the like.
  • the compression rubber layer 12 is provided such that a plurality of V ribs 15 hang down to the belt inner peripheral side.
  • the plurality of V ribs 15 are each formed in a ridge having a substantially inverted triangular cross section extending in the belt length direction, and arranged in parallel in the belt width direction.
  • Each V-rib 15 has, for example, a rib height of 2.0 to 3.0 mm and a width between base ends of 1.0 to 3.6 mm.
  • the number of V ribs is, for example, 3 to 6 (6 in FIG. 1).
  • the compressed rubber layer 12 is formed of a rubber composition in which a rubber component is cross-linked with a cross-linking agent by heating and pressurizing an uncrosslinked rubber composition in which various rubber compounds are blended with a rubber component.
  • the rubber composition for forming the compressed rubber layer 12 may be one obtained by crosslinking an organic peroxide as a crosslinking agent, or one obtained by crosslinking sulfur as a crosslinking agent. Either a sulfur crosslinking agent may be used as a crosslinking agent and the crosslinking may be used.
  • Examples of the rubber component of the rubber composition forming the compression rubber layer 12 include ethylene- ⁇ -olefin elastomers (EPDM, EPR, etc.), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), hydrogenated acrylonitrile rubber. (H-NBR) and the like.
  • the rubber component of the rubber composition forming the compressed rubber layer 12 is preferably the same as the rubber component of the rubber composition forming the adhesive rubber layer 11.
  • Examples of the rubber compound blended in the rubber composition forming the compressed rubber layer 12 include, for example, a reinforcing material such as carbon black, a softening agent, a vulcanization accelerating aid, a processing aid, an anti-aging agent, a co-crosslinking agent, Examples thereof include a crosslinking agent and a vulcanization accelerator.
  • the rubber composition forming the compressed rubber layer 12 may contain short fibers such as nylon short fibers.
  • the short fibers are preferably included in the compressed rubber layer 12 so as to be oriented in the belt width direction, and the short fibers are preferably provided so as to protrude from the surface of the compressed rubber layer 12. .
  • blended the short fiber with the rubber composition which forms the compression rubber layer 12 but the structure which made the short fiber adhere to the surface of the compression rubber layer 12 by flocking etc. may be sufficient.
  • the back reinforcing cloth 13 is made of a cloth material such as a woven fabric, a knitted fabric, or a non-woven fabric formed of yarns such as cotton, polyamide fiber, polyester fiber, and aramid fiber.
  • the thickness of the back reinforcing cloth 13 is, for example, 0.4 to 1.5 mm.
  • the back reinforcing cloth 13 is subjected to a bonding process for bonding to the V-ribbed belt main body 10. Therefore, as shown in FIG. 2, a reinforcing cloth adhesive layer 16 is interposed between the back reinforcing cloth 13 and the adhesive rubber layer 11.
  • the reinforcing cloth adhesive layer 16 includes an RFL layer 16a by an RFL process described later, a soaking rubber layer 16b by a soaking process described later, and a coating rubber layer 16c by a coating process described later from the back reinforcing cloth 13 side. They may be laminated in order to cover the surface of the back reinforcing cloth 13, and the coating rubber layer 16 c may be in contact with the adhesive rubber layer 11. As shown in FIG.
  • the reinforcing cloth adhesive layer 16 covers the surface of the back reinforcing cloth 13 by laminating the RFL layer 16a and the soaking rubber layer 16b in this order from the back reinforcing cloth 13 side, and the soaking rubber layer 16b It may be in contact with the adhesive rubber layer 11.
  • the reinforcing cloth adhesive layer 16 covers the surface of the back reinforcing cloth 13 by sequentially laminating the RFL layer 16a and the coating rubber layer 16c from the back reinforcing cloth 13 side, and the coating rubber layer 16c It may be in contact with the adhesive rubber layer 11.
  • FIG. 3B the reinforcing cloth adhesive layer 16 covers the surface of the back reinforcing cloth 13 by laminating the RFL layer 16a and the soaking rubber layer 16b in this order from the back reinforcing cloth 13 side, and the soaking rubber layer 16b It may be in contact with the adhesive rubber layer 11.
  • the reinforcing cloth adhesive layer 16 covers the surface of the back reinforcing cloth 13 by sequentially laminating the RFL layer
  • the reinforcing cloth adhesive layer 16 is composed of an RFL layer 16 a, and the RFL layer 16 a may be in contact with the adhesive rubber layer 11.
  • the reinforcing cloth adhesive layer 16 may have a primer layer made of epoxy resin or isocyanate resin between the back reinforcing cloth 13 and the RFL layer 16a.
  • the soaking rubber layer 16b and the coating rubber layer 16c include a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer and a vulcanization accelerator having a thiocarbonyl group, and an organic peroxide. It may be formed of a rubber composition cross-linked by.
  • the core wire 14 is composed of a twisted yarn formed of polyamide fiber, polyester fiber, aramid fiber, polyamide fiber or the like.
  • the diameter of the core wire is, for example, 0.5 to 2.5 mm, and the dimension between the centers of adjacent core wires 14 in the belt cross section is, for example, 0.05 to 0.20 mm.
  • the core wire 14 is also subjected to a bonding process for bonding to the V-ribbed belt body 10. Therefore, as shown in FIG. 4, a core wire adhesive layer 17 is interposed between the core wire 14 and the adhesive rubber layer 11.
  • the core wire adhesive layer 17 is formed by sequentially laminating an RFL layer 17a by an RFL process described later and an adhesive rubber layer 17b by a rubber paste process described later from the core wire 14 side.
  • the adhesive rubber layer 11 may be in contact with the adhesive rubber layer 11.
  • the core wire adhesive layer 17 is composed of an RFL layer 17 a, and the RFL layer 17 a may be in contact with the adhesive rubber layer 11.
  • the core wire adhesive layer 17 may have a primer layer made of an epoxy resin or an isocyanate resin between the core wire 14 and the RFL layer 17a.
  • the glue rubber layer 17b is a rubber in which a vulcanization accelerator having a thiocarbonyl group is blended with a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer and is crosslinked with an organic peroxide. It may be formed of a composition.
  • the back reinforcing cloth 13 and the core wire 14 of the fiber member that has been subjected to the adhesion treatment are added to a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer. Since the vulcanization accelerator having a carbonyl group is blended and in contact with the adhesive rubber layer 11 of the rubber member formed of a rubber composition crosslinked with an organic peroxide, the back reinforcing cloth 13 and the core wire 14 High adhesion performance to the adhesive rubber layer 11 can be obtained, and as a result, high durability can be obtained.
  • FIG. 6 shows a pulley layout of an auxiliary drive belt transmission device 20 for an automobile using the V-ribbed belt B according to the first embodiment.
  • the accessory drive belt transmission device 20 is of a serpentine drive type in which a V-ribbed belt B is wound around six pulleys of four rib pulleys and two flat pulleys to transmit power.
  • a power steering pulley 21 of a rib pulley is provided at the uppermost position, and an AC generator pulley 22 of a rib pulley is provided diagonally to the right of the power steering pulley 21. Further, a flat pulley tensioner pulley 23 is provided diagonally to the left of the power steering pulley 21, and a flat pulley water pump pulley 24 is provided below the tensioner pulley 23.
  • a rib pulley crankshaft pulley 25 is provided diagonally to the left of the tensioner pulley 23 and the water pump pulley 24, and a rib pulley air conditioner pulley 26 is provided diagonally to the right of the water pump pulley 24 and the crankshaft pulley 25. It has been.
  • These pulleys are made of, for example, a metal stamped product, a molded product such as a casting, nylon resin, or phenol resin, and have a pulley diameter of 50 to 150 mm.
  • the V-ribbed belt B is wound around the power steering pulley 21 so that the V-rib 15 side comes into contact, and then around the tensioner pulley 23 so that the back surface of the belt comes into contact. After that, it is wound around the crankshaft pulley 25 and the air conditioner pulley 26 in order so that the V-rib 15 side comes into contact, and is further wound around the water pump pulley 24 so that the back surface of the belt comes into contact. Thus, it is wound around the AC generator pulley 22 and finally returned to the power steering pulley 21.
  • the belt span length which is the length of the V-ribbed belt B spanned between the pulleys, is, for example, 50 to 300 mm. Misalignment that can occur between pulleys is 0-2 °.
  • V-ribbed belt B (Manufacturing method of V-ribbed belt B) A method for manufacturing the V-ribbed belt B according to the first embodiment will be described with reference to FIGS.
  • the manufacturing method of the V-ribbed belt B according to Embodiment 1 includes a preparation process, a molding process, a crosslinking process, a grinding process, and a width cutting process.
  • ⁇ Preparation process> -Rubber- A rubber compound is blended with a rubber component and kneaded by a kneader such as a kneader or a Banbury mixer, and the resulting uncrosslinked rubber composition is formed into a sheet shape by calendar molding or the like to form an uncrosslinked rubber for the adhesive rubber layer 11.
  • a sheet 11 ′ is produced.
  • a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer is used, and an organic peroxide and a vulcanization accelerator having a thiocarbonyl group are used as a crosslinking agent.
  • an uncrosslinked rubber sheet 12 ′ for the compressed rubber layer 12 is also produced.
  • short fibers When short fibers are included in the compressed rubber layer 12, short fibers may be blended in the uncrosslinked rubber sheet 12 ′.
  • -Back reinforcement cloth- Adhesion treatment is applied to the back reinforcing cloth 13 '.
  • the RFL treatment in which the back reinforcing cloth 13 ′ is immersed in an RFL aqueous solution and heated the soaking treatment in which the back reinforcing fabric 13 ′ is immersed in a low viscosity soaking agent after the RFL treatment and dried, and the V-ribbed belt after the RFL treatment or after the soaking treatment
  • One or two or more types of adhesive treatment including RFL treatment are applied among coating treatments in which a surface having a main body 10 side, that is, a surface in contact with the adhesive rubber layer 11 is coated with a high viscosity coating agent and dried.
  • the primer process which immerses and heats back reinforcement cloth 13 'in the primer solution of an epoxy or an isocyanate is performed before RFL process.
  • an RF treatment that is immersed and heated in an RF aqueous solution may be performed.
  • an RF treatment that is immersed in an RF aqueous solution and heated before or after the RFL treatment is performed. Also good.
  • the RFL aqueous solution used in the RFL treatment is a mixed aqueous solution in which latex (L) is mixed with an initial condensate of resorcin (R) and formalin (F).
  • the solid content concentration of the RFL aqueous solution is, for example, 3.0 to 30% by mass.
  • Examples of the latex (L) include vinylpyridine / styrene butadiene copolymer rubber (VP-SBR) latex, chloroprene rubber (CR) latex, chlorosulfonated polyethylene rubber (CSM) latex, and 2,3-dichlorobutadiene polymer.
  • Examples thereof include rubber (2,3-DCB) latex, nitrile butadiene rubber (NBR) latex, hydrogenated acrylonitrile butadiene methacrylic acid terpolymer (X-NBR) latex, and the like.
  • vinylpyridine / styrene butadiene copolymer rubber (VP-SBR) latex is preferred.
  • the latex (L) one of the above may be used, or two or more may be used.
  • the immersion time of the back reinforcing cloth 13 ′ in the RFL aqueous solution in the RFL treatment is, for example, 0.5 to 10 seconds
  • the heating temperature after the immersion (heating furnace set temperature) is, for example, 100 to 180 ° C.
  • the heating time is, for example, 30 to 30 600 seconds.
  • the RFL process may be performed once or multiple times. After the RFL treatment, the entire surface of the back reinforcing cloth 13 'is covered with the RFL layer 16a.
  • the amount of the RFL layer 16a attached is, for example, 1 to 40 parts by weight with respect to 100 parts by weight of the back reinforcing cloth 13'. is there.
  • the soaking agent used in the soaking treatment is a solution in which a rubber compound is blended with a rubber component and kneaded with a kneader such as a kneader or a Banbury mixer, and the resulting uncrosslinked rubber composition is dissolved in a solvent such as toluene or methyl ethyl ketone. It is.
  • the solid content concentration of the soaking agent is, for example, 5 to 20% by mass.
  • the rubber component is preferably mainly composed of an ethylene- ⁇ -olefin elastomer, and the rubber component mainly composed of an ethylene- ⁇ -olefin elastomer. More preferably, an organic peroxide is blended as a crosslinking agent and a vulcanization accelerator having a thiocarbonyl group is blended.
  • the immersion time of the back reinforcing cloth 13 ′ after the RFL treatment in the soaking process is, for example, 1 to 30 seconds
  • the drying temperature after the immersion is, for example, 60 to 150 ° C.
  • the drying time is, for example, 10 to 420 seconds.
  • the soaking process may be performed once or a plurality of times. After the soaking process, the entire surface of the back reinforcing cloth 13 ′ is covered with the soaking rubber layer 16b.
  • the amount of the soaking rubber layer 16b is, for example, 5 to 100 mass with respect to 100 parts by mass of the back reinforcing cloth 13 ′. Part.
  • the coating agent used in the coating treatment is a viscosity obtained by mixing a rubber compound with a rubber component and kneading with a kneader such as a kneader or a Banbury mixer, and dissolving the obtained uncrosslinked rubber composition in a solvent such as toluene or methyl ethyl ketone. It is a solid material.
  • the solid content concentration of the coating agent is, for example, 10 to 50% by mass.
  • the rubber component is mainly composed of an ethylene- ⁇ -olefin elastomer as in the case of the adhesive rubber layer 11, and the rubber component mainly composed of ethylene- ⁇ -olefin elastomer. More preferably, an organic peroxide is blended as a crosslinking agent and a vulcanization accelerator having a thiocarbonyl group is blended.
  • Examples of the coating method of the coating agent on the back reinforcing cloth 13 ′ after the RFL treatment or the soaking treatment in the coating treatment include a knife coating method and a roll coating method.
  • the drying temperature after coating (drying furnace set temperature) is, for example, 60 to 150 ° C., and the drying time is, for example, 10 to 600 seconds.
  • the coating process may be performed once or multiple times.
  • the surface of the back reinforcing cloth 13 ′ on the V-ribbed belt body 10 side is covered with the coating rubber layer 16c.
  • the amount of the coating rubber layer 16c attached is 100 parts by mass of the back reinforcing cloth 13 ′. For example, 10 to 250 parts by mass.
  • RFL processing is included among RFL processing in which the core wire 14 'is immersed in an RFL aqueous solution and heated, and rubber paste processing in which the core wire 14' after RFL processing is immersed in rubber paste and dried 1 A seed or two kinds of adhesion treatments are applied.
  • the primer process which immerses and heats core 14 'in the primer solution of an epoxy or isocyanate before RFL process is performed.
  • the RFL aqueous solution used in the RFL treatment is a mixed aqueous solution in which latex (L) is mixed with an initial condensate of resorcin (R) and formalin (F), similarly to the RFL treatment for the back reinforcing cloth 13 '.
  • the solid content concentration of the RFL aqueous solution is, for example, 1 to 30% by mass.
  • Examples of the latex (L) include vinylpyridine / styrene butadiene copolymer rubber (VP-SBR) latex, chloroprene rubber (CR) latex, chlorosulfonated polyethylene rubber (CSM) latex, and 2,3-dichlorobutadiene.
  • examples thereof include polymer rubber (2,3-DCB) latex, nitrile butadiene rubber (NBR) latex, hydrogenated acrylonitrile butadiene methacrylic acid terpolymer (X-NBR) latex, and the like.
  • vinylpyridine / styrene butadiene copolymer rubber (VP-SBR) latex is preferred.
  • the latex (L) one of the above may be used, or two or more may be used.
  • the immersion time of the core wire 14 ′ in the RFL aqueous solution in the RFL treatment is, for example, 0.5 to 5 seconds, the heating temperature (heating furnace set temperature) after the immersion is, for example, 150 to 260 ° C., and the heating time is, for example, 15 to 300. Seconds.
  • the RFL process may be performed once or multiple times. After the RFL treatment, the entire surface of the back reinforcing cloth 13 'is covered with the RFL layer 16a.
  • the amount of the RFL layer 16a attached to 100 parts by mass of the core wire 14 ' is, for example, 0.5 to 15 parts by mass.
  • the rubber paste used in the rubber paste treatment was prepared by mixing a rubber compound with a rubber component and kneading with a kneader such as a kneader or a Banbury mixer, and dissolving the obtained uncrosslinked rubber composition in a solvent such as toluene or methyl ethyl ketone. It is a solution.
  • the solid content concentration of the rubber paste is, for example, 5 to 50% by mass.
  • the rubber component is preferably mainly composed of an ethylene- ⁇ -olefin elastomer, and the rubber component mainly composed of an ethylene- ⁇ -olefin elastomer. More preferably, an organic peroxide is blended as a crosslinking agent and a vulcanization accelerator having a thiocarbonyl group is blended.
  • the immersion time of the core wire 14 'after the RFL treatment in the rubber glue is, for example, 0.5 to 5 seconds
  • the drying temperature after the immersion (drying furnace set temperature) is, for example, 40 to 180 ° C. and the drying time. Is, for example, 15 to 300 seconds.
  • the rubber paste treatment may be performed once or may be performed a plurality of times.
  • the entire surface of the core wire 14 ' is covered with the glue rubber layer 17b.
  • the adhesion amount of the glue rubber layer 17b with respect to 100 parts by mass of the core wire 14 ' is, for example, 0.5 to 70 parts by mass.
  • the uncrosslinked rubber sheet 11 ′ for the adhesive rubber layer 11 is wound so that the drawing direction, which is the drawing direction, corresponds to the belt length direction, and the uncrosslinked rubber sheet 12 ′ for the compressed rubber layer 12 is wound. Is wound so that the reverse direction perpendicular to the direction of the line corresponds to the belt length direction.
  • the rubber sleeve 32 is placed on the belt-forming molded body B ′, and the rubber sleeve 32 is placed and sealed in the vulcanizing can, and the vulcanizing can is filled with high-temperature and high-pressure steam. Hold for a predetermined time. At this time, the cross-linking of the uncrosslinked rubber sheets 11 ′ and 12 ′ proceeds and integrates with the organic peroxide and is combined with the back reinforcing cloth 13 ′ and the core wire 14 ′. As shown in FIG. A cylindrical belt slab S is molded.
  • the V-ribbed belt B according to Embodiment 1 obtained as described above has a back surface reinforcement of a fiber member that has been subjected to one or more types including RFL treatment among RFL treatment, soaking treatment, and coating treatment as an adhesion treatment.
  • Cloth 13 is a rubber member formed of a rubber composition in which a vulcanization accelerator having a thiocarbonyl group is blended with a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer and crosslinked with an organic peroxide.
  • a rubber fiber composite including a structure in which the adhesive rubber layer 11 of the rubber member and the back reinforcing cloth 13 of the fiber member are combined is brought into contact with the adhesive rubber layer 11.
  • the core wire 14 of the fiber member to which one or two types including the RFL treatment out of the RFL treatment and the rubber paste treatment as the adhesion treatment is provided is an ethylene- ⁇ -olefin elastomer.
  • the adhesive rubber layer 11 of the rubber member formed of a rubber composition which is blended with a vulcanization accelerator having a thiocarbonyl group and is crosslinked with an organic peroxide.
  • the rubber fiber composite body includes a structure in which the adhesive rubber layer 11 of the rubber member and the core wire 14 of the fiber member are combined.
  • the V-ribbed belt B (rubber fiber composite) according to the second embodiment has the same external configuration as that of the first embodiment.
  • the V-ribbed belt B according to the second embodiment will be described using the same drawings and the same reference numerals as those of the first embodiment.
  • the adhesive rubber layer 11 heats and pressurizes an uncrosslinked rubber composition in which various rubber compounds are blended with the rubber component and crosslinks the rubber component with a crosslinking agent.
  • the rubber composition is formed.
  • the rubber composition for forming the adhesive rubber layer 11 may be one obtained by crosslinking an organic peroxide as a crosslinking agent, or one obtained by crosslinking sulfur as a crosslinking agent. Either a sulfur crosslinking agent may be used as a crosslinking agent and the crosslinking may be used.
  • Examples of the rubber component of the rubber composition forming the adhesive rubber layer 11 include ethylene- ⁇ -olefin elastomers (EPDM, EPR, etc.), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), and hydrogenated acrylonitrile rubber. (H-NBR) and the like.
  • EPDM ethylene- ⁇ -olefin elastomers
  • CR chloroprene rubber
  • CSM chlorosulfonated polyethylene rubber
  • H-NBR hydrogenated acrylonitrile rubber
  • Examples of the rubber compound to be blended in the rubber composition forming the adhesive rubber layer 11 include, for example, a reinforcing material such as carbon black, a softening agent, a vulcanization acceleration aid, a processing aid, an antiaging agent, a co-crosslinking agent, Examples thereof include a crosslinking agent and a vulcanization accelerator.
  • the back reinforcing cloth 13 is subjected to a bonding process for bonding to the V-ribbed belt main body 10. Therefore, as shown in FIG. 2, a reinforcing cloth adhesive layer 16 is interposed between the back reinforcing cloth 13 and the adhesive rubber layer 11. As shown in FIG. 3A, the reinforcing cloth adhesive layer 16 has an RFL layer 16 a by RFL treatment, a soaking rubber layer 16 b by soaking treatment, and a coating rubber layer 16 c by coating treatment laminated in this order from the back reinforcing fabric 13 side. The surface of the cloth 13 is covered, so that the RFL layer 16a may be in contact with the soaking rubber layer 16b. As shown in FIG.
  • the reinforcing cloth adhesive layer 16 covers the surface of the back reinforcing cloth 13 by laminating the RFL layer 16a and the soaking rubber layer 16b in this order from the back reinforcing cloth 13 side, so that the RFL layer 16a is soaked. It may be in contact with the rubber layer 16b.
  • the reinforcing cloth adhesive layer 16 may have a primer layer made of epoxy resin or isocyanate resin between the back reinforcing cloth 13 and the RFL layer 16a.
  • the soaking rubber layer 16b is formed of a rubber composition in which a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer is blended with a vulcanization accelerator having a thiocarbonyl group and is crosslinked with an organic peroxide. .
  • the rubber composition forming the soaking rubber layer 16b has the same configuration as the rubber composition forming the adhesive rubber layer 11 in the first embodiment.
  • the coating rubber layer 16c is a rubber in which a vulcanization accelerator having a thiocarbonyl group is blended with a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer and is crosslinked with an organic peroxide. It may be formed of a composition.
  • the core wire 14 is also subjected to a bonding process for bonding to the V-ribbed belt body 10. Therefore, as shown in FIG. 4, a core wire adhesive layer 17 is interposed between the core wire 14 and the adhesive rubber layer 11.
  • the core wire adhesive layer 17 covers the surface of the core wire 14 by laminating an RFL layer 17 a by RFL treatment and a glue rubber layer 17 b by rubber paste treatment in order from the core wire 14 side. Also good.
  • the core wire adhesive layer 17 may be composed of an RFL layer 17a.
  • the core wire adhesive layer 17 may have a primer layer made of an epoxy resin or an isocyanate resin between the core wire 14 and the RFL layer 17a.
  • the glue rubber layer 17b is a rubber in which a vulcanization accelerator having a thiocarbonyl group is blended with a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer and is crosslinked with an organic peroxide. It may be formed of a composition.
  • the soaking agent used in the soaking treatment of the back reinforcing cloth 13 ′ is a rubber component mainly composed of ethylene- ⁇ -olefin elastomer, an organic peroxide and thiocarbonyl as a crosslinking agent. It is a solution in which a rubber compound containing a vulcanization accelerator having a group is mixed and kneaded with a kneader such as a kneader or a Banbury mixer, and the resulting uncrosslinked rubber composition is dissolved in a solvent such as toluene or methyl ethyl ketone. .
  • the V-ribbed belt B according to the second embodiment obtained as described above has an ethylene- ⁇ -between the adhesive rubber layer 11 of the rubber member and the back reinforcing cloth 13 of the fiber member subjected to the RFL treatment as the adhesion treatment.
  • a rubber component mainly composed of an olefin elastomer is blended with a vulcanization accelerator having a thiocarbonyl group, and has a soaking rubber layer 16b formed of a rubber composition cross-linked with an organic peroxide.
  • the back reinforcing fabric 13 of the treated fiber member was blended with a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer and a vulcanization accelerator having a thiocarbonyl group and crosslinked with an organic peroxide.
  • the rubber composition is in contact with the rubber composition and includes a structure in which the adhesive rubber layer 11 of the rubber member and the back reinforcing cloth 13 of the fiber member are combined. .
  • the V-ribbed belt B (rubber fiber composite) according to the third embodiment has the same external configuration as that of the first embodiment.
  • the V-ribbed belt B according to the third embodiment will be described using the same drawings and the same reference numerals as those of the first embodiment.
  • the adhesive rubber layer 11 heats and pressurizes an uncrosslinked rubber composition in which various rubber compounds are blended with the rubber component and crosslinks the rubber component with a crosslinking agent.
  • the rubber composition is formed.
  • the rubber composition for forming the adhesive rubber layer 11 may be one obtained by crosslinking an organic peroxide as a crosslinking agent, or one obtained by crosslinking sulfur as a crosslinking agent. Either a sulfur crosslinking agent may be used as a crosslinking agent and the crosslinking may be used.
  • Examples of the rubber component of the rubber composition forming the adhesive rubber layer 11 include ethylene- ⁇ -olefin elastomers (EPDM, EPR, etc.), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), and hydrogenated acrylonitrile rubber. (H-NBR) and the like.
  • EPDM ethylene- ⁇ -olefin elastomers
  • CR chloroprene rubber
  • CSM chlorosulfonated polyethylene rubber
  • H-NBR hydrogenated acrylonitrile rubber
  • Examples of the rubber compound to be blended in the rubber composition forming the adhesive rubber layer 11 include, for example, a reinforcing material such as carbon black, a softening agent, a vulcanization acceleration aid, a processing aid, an antiaging agent, a co-crosslinking agent, Examples thereof include a crosslinking agent and a vulcanization accelerator.
  • the back reinforcing cloth 13 is subjected to a bonding process for bonding to the V-ribbed belt main body 10. Therefore, as shown in FIG. 2, a reinforcing cloth adhesive layer 16 is interposed between the back reinforcing cloth 13 and the adhesive rubber layer 11. As shown in FIG. 3A, the reinforcing cloth adhesive layer 16 has an RFL layer 16 a by RFL treatment, a soaking rubber layer 16 b by soaking treatment, and a coating rubber layer 16 c by coating treatment laminated in this order from the back reinforcing fabric 13 side. The surface of the cloth 13 is covered, so that the soaking rubber layer 16b may be in contact with the coating rubber layer 16c. As shown in FIG.
  • the reinforcing cloth adhesive layer 16 covers the surface of the back reinforcing cloth 13 by laminating the RFL layer 16a and the coating rubber layer 16c in this order from the back reinforcing cloth 13, so that the RFL layer 16a is coated. It may be in contact with the rubber layer 16c.
  • the reinforcing cloth adhesive layer 16 may have a primer layer made of epoxy resin or isocyanate resin between the back reinforcing cloth 13 and the RFL layer 16a.
  • the coating rubber layer 16c is formed of a rubber composition in which a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer is blended with a vulcanization accelerator having a thiocarbonyl group and is crosslinked with an organic peroxide. .
  • the rubber composition forming the coating rubber layer 16c has the same configuration as the rubber composition forming the adhesive rubber layer 11 in the first embodiment.
  • the core wire 14 is also subjected to a bonding process for bonding to the V-ribbed belt body 10. Therefore, as shown in FIG. 4, a core wire adhesive layer 17 is interposed between the core wire 14 and the adhesive rubber layer 11.
  • the core wire adhesive layer 17 covers the surface of the core wire 14 by laminating an RFL layer 17 a by RFL treatment and a glue rubber layer 17 b by rubber paste treatment in order from the core wire 14 side. Also good.
  • the core wire adhesive layer 17 may be composed of an RFL layer 17a.
  • the core wire adhesive layer 17 may have a primer layer made of an epoxy resin or an isocyanate resin between the core wire 14 and the RFL layer 17a.
  • the glue rubber layer 17b is a rubber in which a vulcanization accelerator having a thiocarbonyl group is blended with a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer and is crosslinked with an organic peroxide. It may be formed of a composition.
  • the coating agent used in the coating treatment of the back reinforcing fabric 13 ′ is a rubber component mainly composed of ethylene- ⁇ -olefin elastomer, an organic peroxide and thiocarbonyl as a crosslinking agent.
  • the V-ribbed belt B according to the third embodiment obtained as described above is between the adhesive rubber layer 11 of the rubber member and the back reinforcing cloth 13 of the fiber member subjected to the RFL treatment or the RFL treatment and the soaking treatment as the adhesion treatment.
  • a coating rubber layer 16c formed of a rubber composition in which a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer is blended with a vulcanization accelerator having a thiocarbonyl group and crosslinked with an organic peroxide is formed.
  • the back reinforcing cloth 13 of the fiber member that has been subjected to adhesion treatment is blended with a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer, a vulcanization accelerator having a thiocarbonyl group, and an organic peroxide.
  • a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer, a vulcanization accelerator having a thiocarbonyl group, and an organic peroxide.
  • the V-ribbed belt B (rubber fiber composite) according to the fourth embodiment has the same external configuration as that of the first embodiment.
  • the V-ribbed belt B according to the fourth embodiment will be described using the same drawings and the same reference numerals as those of the first embodiment.
  • the adhesive rubber layer 11 heats and pressurizes an uncrosslinked rubber composition in which various rubber compounds are blended with the rubber component and crosslinks the rubber component with a crosslinking agent.
  • the rubber composition is formed.
  • the rubber composition for forming the adhesive rubber layer 11 may be one obtained by crosslinking an organic peroxide as a crosslinking agent, or one obtained by crosslinking sulfur as a crosslinking agent. Either a sulfur crosslinking agent may be used as a crosslinking agent and the crosslinking may be used.
  • Examples of the rubber component of the rubber composition forming the adhesive rubber layer 11 include ethylene- ⁇ -olefin elastomers (EPDM, EPR, etc.), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), and hydrogenated acrylonitrile rubber. (H-NBR) and the like.
  • EPDM ethylene- ⁇ -olefin elastomers
  • CR chloroprene rubber
  • CSM chlorosulfonated polyethylene rubber
  • H-NBR hydrogenated acrylonitrile rubber
  • Examples of the rubber compound to be blended in the rubber composition forming the adhesive rubber layer 11 include, for example, a reinforcing material such as carbon black, a softening agent, a vulcanization acceleration aid, a processing aid, an antiaging agent, a co-crosslinking agent, Examples thereof include a crosslinking agent and a vulcanization accelerator.
  • the core wire 14 is subjected to a bonding process for bonding to the V-ribbed belt main body 10. Therefore, as shown in FIG. 4, a core wire adhesive layer 17 is interposed between the core wire 14 and the adhesive rubber layer 11. As shown in FIG. 5A, the core wire adhesive layer 17 covers the surface of the core wire 13 by laminating an RFL layer 17a by RFL treatment and a glue rubber layer 17b by rubber paste treatment in order from the core wire 14 side. The RFL layer 17a is in contact with the glue rubber layer 17b.
  • the core wire adhesive layer 17 may have a primer layer made of an epoxy resin or an isocyanate resin between the core wire 14 and the RFL layer 17a.
  • the glue rubber layer 17b is formed of a rubber composition in which a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer is blended with a vulcanization accelerator having a thiocarbonyl group and is crosslinked with an organic peroxide. .
  • the rubber composition forming the glue rubber layer 17b has the same configuration as the rubber composition forming the adhesive rubber layer 11 in the first embodiment.
  • the rubber paste used for the rubber paste treatment of the core wire 14 ′ is composed of a rubber component mainly composed of ethylene- ⁇ -olefin elastomer, an organic peroxide and thiocarbonyl as a crosslinking agent. It is a solution in which a rubber compound containing a vulcanization accelerator having a group is mixed and kneaded with a kneader such as a kneader or a Banbury mixer, and the resulting uncrosslinked rubber composition is dissolved in a solvent such as toluene or methyl ethyl ketone. .
  • the V-ribbed belt B according to Embodiment 4 obtained as described above has an ethylene- ⁇ -olefin between the adhesive rubber layer 11 of the rubber member and the core wire 14 of the fiber member that has been subjected to RFL treatment as the adhesion treatment.
  • the core wire 14 of the fiber member that has been subjected to the adhesion treatment is blended with a rubber component mainly composed of an ethylene- ⁇ -olefin elastomer and a vulcanization accelerator having a thiocarbonyl group, and is crosslinked with an organic peroxide.
  • the rubber composition is in contact with the rubber composition and includes a structure in which the adhesive rubber layer 11 of the rubber member and the core wire 14 of the fiber member are combined.
  • the V-ribbed belt B is used as an example.
  • the transmission belt constitutes a rubber fiber composite including a structure in which a rubber member and a fiber member subjected to an adhesion treatment are combined
  • these belts For example, a low-edge type V-belt B as shown in FIG. 12A or a wrapped V-belt B as shown in FIG. 12B may be used, as shown in FIG. 12C. It may be a flat belt B or a toothed belt B as shown in FIG. 12D.
  • it comprises the rubber fiber composite containing the structure which the rubber member and the fiber member to which the adhesion
  • V-ribbed belt V-ribbed belts of the following Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4 were manufactured in the same manner as in the first embodiment. In addition, it shows also in Table 1 about the mixing
  • EPDM (trade name: EP33, manufactured by JSR Co., Ltd., ethylene content: 52 mass%, ethylidene nobornene (diene component) content: 8.1 mass%, Mooney viscosity: 28 ML 1 + 4 (125 ° C.
  • the content of the organic peroxide is 0.81% by mass
  • the content of sulfur is 0.94% by mass
  • the content of the thiuram vulcanization accelerator is 0.00. 47% by mass, sulfur content / organic peroxide content 1.16, thiuram vulcanization accelerator content / organic peroxide content 0.58, and thiuram type
  • the content of the vulcanization accelerator / the content of sulfur is 0.5.
  • EPDM (trade name: EP22, manufactured by JSR Corporation, ethylene content: 54 mass%, ethylidene nobornene (diene component) content: 4.5 mass%, Mooney viscosity: 27 ML 1 + 4 (125 ° C.
  • a rubber component As a rubber component, with respect to 100 parts by mass of the rubber component, 65 parts by mass of carbon black as a reinforcing material (trade name: Diamond Black H) manufactured by Mitsubishi Chemical Co., Ltd., process oil as a softener (trade name manufactured by Nippon Sun Oil Co., Ltd.) : Samper 2280) 10 parts by mass, zinc oxide (3 types of zinc oxide manufactured by Hakusui Chemical Co., Ltd.) as a vulcanization accelerator, 1 part by mass of processing aid stearic acid (Stearic acid S50 manufactured by Shin Nippon Rika Co., Ltd.), 2 parts by mass of a benzimidazole anti-aging agent (trade name: NOCRACK MB, manufactured by Ouchi Shinsei Chemical Co., Ltd.), sulfur as a crosslinking agent (trade name: Seimi OT, manufactured by Nihon Kiboshi Kogyo Co., Ltd.) 2 1 part by mass, 1 part by mass of a thiuram vulcanization accelerator
  • the uncrosslinked rubber sheet for the compression rubber layer has a higher ethylene content in EPDM as the rubber component and lower ethylidene nobornene (diene component) content and Mooney viscosity than the uncrosslinked rubber sheet for the adhesive rubber layer. Also, unlike the uncrosslinked rubber sheet for the adhesive rubber layer, only sulfur as a crosslinking agent is blended and no organic peroxide is blended. On the other hand, the same thiocarbonyl as the uncrosslinked rubber sheet for the adhesive rubber layer A thiuram vulcanization accelerator having a group is blended.
  • a woven fabric made of cotton / polyester blended fiber was used as the back reinforcing fabric.
  • the back reinforcing fabric was subjected to an adhesion treatment including RFL treatment, soaking treatment, and coating treatment.
  • RFL resorcin
  • F formalin
  • R resorcin
  • F formalin
  • a mixture of an aged RF aqueous solution and a latex (L) vinylpyridine / styrene butadiene copolymer rubber (VP-SBR) latex (trade name: JSR-0652, manufactured by JSR Corporation) was used.
  • the immersion time of the back reinforcing cloth in the RFL aqueous solution in the RFL treatment was 6 seconds, the heating temperature after heating (heating furnace set temperature) was 150 ° C., and the heating time was 300 seconds.
  • the adhesion amount of the RFL layer with respect to 100 parts by mass of the back reinforcing cloth was 13 parts by mass.
  • EPDM (trade name: Nordel IP4640, ethylene content: 55% by mass, ethylidene nobornene (diene component) content: 4.9% by mass, Mooney viscosity: 40 ML 1 + 4 (125 ° C.)
  • a rubber component with respect to 100 parts by mass of the rubber component, 40 parts by mass of reinforcing material carbon black (trade name: Diamond Black H) manufactured by Mitsubishi Chemical Co., Ltd., silica of reinforcing material (product name: Ultrasil VN3 manufactured by Evonik) ) 40 parts by mass, 5 parts by mass of softening agent process oil (trade name: Samper 2280 manufactured by Nippon Sun Oil Co., Ltd.), 5 parts by mass of zinc oxide (3 types of zinc oxide manufactured by Hakusui Chemical Co., Ltd.) 1 part by weight of stearic acid (manufactured by Shin Nippon Rika Co., Ltd., stearic acid S50),
  • product name: NOCRACK MB NOCRACK MB 2 parts by mass
  • cross-linking agent sulfur trade name: Oil Sulfur manufactured by Hosoi Chemical Industry Co., Ltd.
  • thiuram vulcanization accelerator having a thiocarbonyl group large A product obtained by dissolving an uncrosslinked rubber composition kneaded with a Banbury mixer by blending 1 part by mass of Uchinsei Chemical Co., Ltd. (trade name: Noxeller TET) was used.
  • the solid content concentration of the soaking agent was 15% by mass.
  • the immersion time of the back reinforcing cloth in the soaking treatment in the soaking treatment was 6 seconds
  • the drying temperature after the immersion was 130 ° C.
  • the drying time was 100 seconds.
  • the amount of the soaking rubber layer attached to 100 parts by mass of the back reinforcing cloth was 16 parts by mass.
  • EPDM (trade name: Nordel IP4640 manufactured by DOW CHEMICAL) is used as a coating agent as a coating agent, and carbon black as a reinforcing material (trade name: Diamond Black H, manufactured by Mitsubishi Chemical Corporation) with respect to 100 parts by mass of the rubber component.
  • silica of reinforcing material (trade name: Ultrazil VN3, manufactured by Evonik), 5 parts by mass of process oil of softener (trade name: Samper 2280, manufactured by Nippon San Oil Co., Ltd.), vulcanization accelerator 5 parts by weight of zinc oxide (manufactured by Hakusui Chemical Co., Ltd., 3 types of zinc oxide), 1 part by weight of processing aid stearic acid (manufactured by Shin Nippon Rika Co., Ltd., stearic acid S50), benzimidazole anti-aging agent (manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • Polyester fiber twisted yarn was used as the core wire.
  • the core wire was subjected to adhesion treatment including primer treatment and RFL treatment.
  • a solution having a solid content concentration of 13% by mass in which polymethylene polyphenyl polyisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumidur 44V20) was dissolved in toluene was used as the primer solution.
  • the immersion time of the core wire in the primer solution was 3 seconds, the heating temperature after the immersion (heating furnace set temperature) was 220 ° C., and the heating time was 80 seconds.
  • the amount of the primer layer attached to 100 parts by mass of the core wire was 6 parts by mass.
  • RFL resorcin
  • F formalin
  • R resorcin
  • F formalin
  • a mixture of an aged RF aqueous solution and a latex (L) vinylpyridine / styrene butadiene copolymer rubber (VP-SBR) latex (trade name: JSR-0652, manufactured by JSR Corporation) was used.
  • the immersion time of the core wire in the RFL aqueous solution was 3 seconds, the heating temperature after immersion (heating furnace set temperature) was 240 ° C., and the heating time was 80 seconds.
  • the adhesion amount of the RFL layer with respect to 100 parts by mass of the core wire was 5 parts by mass.
  • the V-ribbed belt of Example 1-1 had a belt length of 1115 mm, a belt width of 10.68 mm (three ribs), a belt thickness of 4.3 mm, and a V-rib height of 2.0 mm.
  • Example 1-2 For the uncrosslinked rubber sheet for the adhesive rubber layer, a dithiocarbamate vulcanization accelerator having a thiocarbonyl group (trade name: Noxeller EZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.) was blended in place of the thiuram vulcanization accelerator. Except for the above, a V-ribbed belt having the same configuration as Example 1-1 was designated as Example 1-2.
  • the content of the organic peroxide is 0.81% by mass
  • the content of sulfur is 0.94% by mass
  • the content of the thiuram vulcanization accelerator is 0.00. 47% by mass, sulfur content / organic peroxide content 1.16, thiuram vulcanization accelerator content / organic peroxide content 0.58, and thiuram type
  • the content of the vulcanization accelerator / the content of sulfur is 0.5.
  • Example 1-3 For the uncrosslinked rubber sheet for the adhesive rubber layer, a V-ribbed belt having the same configuration as Example 1-1 was used as Example 1-3 except that the amount of sulfur was 1 part by mass with respect to 100 parts by mass of the rubber component. .
  • the content of the organic peroxide is 0.81% by mass
  • the content of sulfur is 0.47% by mass
  • the content of the thiuram vulcanization accelerator is 0.00. 47 mass%
  • sulfur content / organic peroxide content is 0.58
  • thiuram vulcanization accelerator content / organic peroxide content is 0.58
  • thiuram type The content of vulcanization accelerator / the content of sulfur is 1.
  • Example 1-4 For the uncrosslinked rubber sheet for the adhesive rubber layer, a V-ribbed belt having the same configuration as that of Example 1-1 except that sulfur was not blended was determined as Example 1-4.
  • the content of the organic peroxide is 0.82% by mass
  • the content of the thiuram vulcanization accelerator is 0.48% by mass
  • the content of the sulfur accelerator / the content of the organic peroxide is 0.59.
  • Comparative Example 1-2 For the uncrosslinked rubber sheet for the adhesive rubber layer, a V-ribbed belt having the same configuration as that of Example 1-1 except that no organic peroxide was blended was used as Comparative Example 1-2.
  • the plate rubber 41 is fixed to one chuck of the tensile tester, and every other one of the seven core wires 42 embedded in the plate rubber 41 on the other chuck.
  • the three core wires 42 arranged are pulled out and fixed in a direction forming an angle of 90 ° with respect to the plate rubber 41, the peeling speed is 50 mm / min, and the three core wires 42 from the plate rubber 41 are 100 mm. It peeled. The average of the peak values between the peeling lengths of 10 to 100 mm was taken as the peeling adhesive strength. Moreover, the peeling state was observed visually.
  • FIG. 14 shows a pulley layout of the belt test traveling machine 50.
  • a large-diameter driven pulley 51 and a driving pulley 52 are provided at intervals in the vertical direction, and the pulley diameter is 85 mm in the middle in the vertical direction.
  • An idler pulley 53 that is a flat pulley is provided, and a small-diameter driven pulley 54 that is a rib pulley having a pulley diameter of 45 mm is provided on the right side of the idler pulley 53.
  • the idler pulley 53 is positioned so that the winding angle of the V-ribbed belt B is 120 °, and the small-diameter driven pulley 54 is positioned so that the winding angle of the V-ribbed belt B is 90 °.
  • a rotation load corresponding to 8.9 kW is applied to the large-diameter driven pulley 51.
  • the small-diameter driven pulley 54 is configured to be movable in the lateral direction so that belt tension can be applied to the V-ribbed belt B.
  • the V-ribbed belt B is in contact with the large-diameter driven pulley 51, the driving pulley 52, and the small-diameter driven pulley 54 on the V-rib side, and is in contact with the idler pulley 53 on the back side. Wrapped like so.
  • Each of the V-ribbed belts B of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4 is set in the belt running test machine 50, and a small-diameter driven pulley so that the belt tension is applied.
  • a dead weight of 588 N was loaded on the side 54, and the belt was run by rotating the drive pulley 52 at a rotational speed of 4900 rpm under an atmospheric temperature of 120 ° C.
  • the longest running time was set to 150 hours, and those that were damaged within 150 hours were checked for running life and failure mode.
  • Examples 1-1 to 1 were formed with the rubber composition of EPDM in which the adhesive rubber layer was blended with a vulcanization accelerator having a thiocarbonyl group and crosslinked with an organic peroxide.
  • -4 is other than Comparative Example 1-1 in which a vulcanization accelerator having a thiocarbonyl group is not blended, Comparative Example 1-2 not crosslinked by an organic peroxide, and a vulcanization accelerator having a thiocarbonyl group
  • Comparative Examples 1-3 and 1-4 in which the vulcanization accelerator is blended, it can be seen that the adhesive strength of the core wire to the adhesive rubber layer is high, and the durability of the belt running is high.
  • V-ribbed belt V-ribbed belts of the following Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4 were produced in the same manner as in the first embodiment.
  • Table 4 also shows the composition of the uncrosslinked rubber composition contained in the rubber paste used in the rubber paste treatment of the core wire.
  • Example 2-1> A polyester fiber twisted yarn was used as the core wire.
  • the core wire was subjected to adhesion treatment including primer treatment, RFL treatment, and rubber paste treatment.
  • a solution having a solid content concentration of 13% by mass in which polymethylene polyphenyl polyisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumidur 44V20) was dissolved in toluene was used as the primer solution.
  • the immersion time of the core wire in the primer solution was 3 seconds
  • the heating temperature after the immersion (heating furnace set temperature) was 220 ° C.
  • the heating time was 80 seconds.
  • the adhesion amount of the primer layer with respect to 100 parts by mass of the core wire was 5 parts by mass.
  • RFL resorcin
  • F formalin
  • R resorcin
  • F formalin
  • a mixture of an aged RF aqueous solution and a latex (L) vinylpyridine / styrene butadiene copolymer rubber (VP-SBR) latex (trade name: JSR-0652, manufactured by JSR Corporation) was used.
  • the immersion time of the core wire in the RFL aqueous solution was 3 seconds, the heating temperature after immersion (heating furnace set temperature) was 240 ° C., and the heating time was 80 seconds.
  • the adhesion amount of the RFL layer with respect to 100 parts by mass of the core wire was 5 parts by mass.
  • EPDM (trade name: Nordel IP4640 manufactured by DOW CHEMICAL) is used as the rubber component
  • carbon black Mitsubishi Chemical Co., Ltd., product name: diamond black
  • a reinforcing material is used for 100 parts by mass of the rubber component.
  • silica of reinforcing material (trade name: Ultrazil VN3, manufactured by Evonik), 5 parts by mass of softening agent process oil (trade name: Samper 2280, manufactured by Nippon San Oil Co., Ltd.), vulcanization acceleration aid 5 parts by weight of zinc oxide (manufactured by Hakusui Chemical Co., Ltd., 3 types of zinc oxide), 1 part by weight of processing aid stearic acid (Stearic acid S50 by Shin Nippon Chemical Co., Ltd.), benzimidazole anti-aging agent (Ouchi Shinsei Chemical Co., Ltd.) Product name: NOCRACK MB) 2 parts by mass, co-crosslinking agent (trade name: High Cross M, manufactured by Seiko Chemical Co., Ltd.), 2 parts by mass, presence of crosslinking agent Peroxide (made by NOF Corporation, trade name: peroximon F40, purity 40% by mass) 4.3 parts by mass, crosslinking agent sulfur (trade name: oil sulfur produced by Hoso
  • the solid content concentration of the rubber paste was 20% by mass.
  • the organic peroxide content is 0.85% by mass
  • the sulfur content is 0.99% by mass
  • the thiuram vulcanization accelerator content is 0.50% by mass.
  • sulfur content / organic peroxide content 1.16, thiuram vulcanization accelerator content / organic peroxide content 0.59, and thiuram vulcanization accelerator Content / sulfur content is 0.51.
  • the immersion time of the core wire in the rubber paste in the rubber paste treatment was 6 seconds
  • the drying temperature after the immersion (drying furnace setting temperature) was 60 ° C.
  • the drying time was 80 seconds.
  • the adhesion amount of the glue rubber layer with respect to 100 parts by mass of the core wire was 7 parts by mass.
  • EPDM (trade name: EP33, manufactured by JSR) is used as a rubber component
  • carbon black (trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.) with respect to 100 parts by mass of the rubber component.
  • silica of reinforcing material (trade name: Ultrazil VN3, manufactured by Evonik), 15 parts by mass of process oil of softener (trade name: Samper 2280, manufactured by Nippon San Oil Co., Ltd.), vulcanization accelerator 5 parts by weight of zinc oxide (manufactured by Hakusui Chemical Co., Ltd., 3 types of zinc oxide), 1 part by weight of processing aid stearic acid (manufactured by Shin Nippon Rika Co., Ltd., stearic acid S50), benzimidazole anti-aging agent (manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • NOCRACK MB NOCRACK MB 2 parts by mass
  • sulfur as a cross-linking agent product name: Seimi OT, manufactured by Nihon Kiboshi Kogyo Co., Ltd.
  • thiocarbonyl group Ram vulcanization accelerator manufactured by Ouchi Shinko Chemical Industrial Co., trade name: Nocceler TET
  • the uncrosslinked rubber sheet for the compression rubber layer and the back reinforcing fabric used had the same configuration as in Example 1-1.
  • the V-ribbed belt of Example 2-1 had a belt length of 1115 mm, a belt width of 10.68 mm (three ribs), a belt thickness of 4.3 mm, and a V-rib height of 2.0 mm.
  • Example 2-2 For the rubber paste used for the rubber paste treatment of the core wire, a dithiocarbamate vulcanization accelerator having a thiocarbonyl group (trade name: Noxeller EZ manufactured by Ouchi Shinsei Chemical Co., Ltd.) is used instead of the thiuram vulcanization accelerator.
  • a V-ribbed belt having the same configuration as that of Example 2-1 was determined as Example 2-2 except that.
  • the organic peroxide content is 0.85% by mass
  • the sulfur content is 0.99% by mass
  • the thiuram vulcanization accelerator content is 0.50% by mass.
  • sulfur content / organic peroxide content 1.16, thiuram vulcanization accelerator content / organic peroxide content 0.59, and thiuram vulcanization accelerator Content / sulfur content is 0.51.
  • Example 2-3 Regarding the rubber paste used for the rubber paste treatment of the core wire, a V-ribbed belt having the same configuration as that of Example 2-1 except that the amount of sulfur is 1 part by mass with respect to 100 parts by mass of the rubber component is the same as Example 2-3. did.
  • the organic peroxide content is 0.85% by mass
  • the sulfur content is 0.50% by mass
  • the thiuram vulcanization accelerator content is 0.50% by mass.
  • sulfur content / organic peroxide content is 0.59
  • thiuram vulcanization accelerator content / organic peroxide content is 0.59
  • thiuram vulcanization accelerator Content / sulfur content is 1.
  • Example 2-4 is a V-ribbed belt having the same configuration as Example 2-1 except that sulfur is not blended in the rubber paste used for the rubber paste treatment of the core wire.
  • the content of the organic peroxide is 0.86% by mass
  • the content of the thiuram vulcanization accelerator is 0.50% by mass
  • Content / content of organic peroxide is 0.58.
  • Comparative Example 2-1 A V-ribbed belt having the same configuration as that of Example 2-1 except that sulfur and a thiuram vulcanization accelerator were not blended was used as Comparative Example 2-1 for rubber paste used for the rubber paste treatment of the core wire.
  • Comparative Example 2-2 A V-ribbed belt having the same configuration as that of Example 2-1 except that no organic peroxide was blended was used as Comparative Example 2-2, except that the rubber paste used for the rubber paste treatment of the core wire was not blended.
  • EPDM (trade name: EP33, manufactured by JSR Corporation) is used as a rubber component, and carbon black (Tokai) as a reinforcing material is added to 100 parts by mass of the rubber component
  • Carbon (trade name: Seast SO) 40 parts by weight, silica (Evonik, trade name: Ultrazil VN3) 40 parts by weight, softener process oil (trade name: Sunper 2280) 15 5 parts by mass of zinc oxide (3 types of zinc oxide manufactured by Hakusui Chemical Co., Ltd.), 1 part by mass of stearic acid (Stearic acid S50 manufactured by Shin Nippon Rika Co., Ltd.), benzimidazole anti-aging agent 2 parts by weight of agent (trade name: NOCRACK MB, manufactured by Ouchi Shinsei Chemical Co., Ltd.)
  • Organic peroxide cross-linked uncrosslinked rubber sheet containing 4.3 parts by weight of peroxide (trade name: Peroximon F40, purity 40%
  • Tables 5 and 6 show the test results.
  • Example 2 in which the cord rubber layer was formed of an EPDM rubber composition blended with a vulcanization accelerator having a thiocarbonyl group and crosslinked with an organic peroxide.
  • 1 to 2-4 are Comparative Example 2-1 in which a vulcanization accelerator having a thiocarbonyl group is not blended, Comparative Example 2-2 not crosslinked with an organic peroxide, and vulcanization having a thiocarbonyl group Compared with Comparative Examples 2-3 and 2-4 in which a vulcanization accelerator other than the accelerator is blended, the adhesive strength to any rubber composition of the sulfur vulcanization system and the organic peroxide vulcanization system is high. It can be seen that the durability of the belt running is high.
  • the present invention is useful in the technical field of rubber fiber composites such as transmission belts and methods for producing the same.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un composite caoutchouc-fibre (B) qui comprend une structure obtenue par combinaison d'un élément en caoutchouc (11) et d'éléments en fibres traitées avec un adhésif (13, 14). Les éléments en fibres traitées avec un adhésif (13, 14) sont en contact avec une composition de caoutchouc qui est obtenue par mélange d'un accélérateur de vulcanisation comportant des groupes thiocarbonyle avec un composant de caoutchouc comprenant principalement un élastomère d'éthylène-α-oléfine, et qui est réticulée par un peroxyde organique.
PCT/JP2015/004461 2014-09-09 2015-09-02 Composite caoutchouc-fibre WO2016038854A1 (fr)

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CN109073040A (zh) * 2016-04-15 2018-12-21 三之星机带株式会社 摩擦传动带
EP3444500A4 (fr) * 2016-04-15 2020-01-01 Mitsuboshi Belting Ltd. Courroie de transmission à frottement
KR20200091923A (ko) * 2017-12-13 2020-07-31 게이츠 코포레이션 배면 직물을 지닌 치형 전동 벨트
JP2020525344A (ja) * 2017-06-30 2020-08-27 コーロン インダストリーズ インク 軽量化されたゴム補強材の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109073040A (zh) * 2016-04-15 2018-12-21 三之星机带株式会社 摩擦传动带
EP3444500A4 (fr) * 2016-04-15 2020-01-01 Mitsuboshi Belting Ltd. Courroie de transmission à frottement
JP2020525344A (ja) * 2017-06-30 2020-08-27 コーロン インダストリーズ インク 軽量化されたゴム補強材の製造方法
JP7128218B2 (ja) 2017-06-30 2022-08-30 コーロン インダストリーズ インク 軽量化されたゴム補強材の製造方法
KR20200091923A (ko) * 2017-12-13 2020-07-31 게이츠 코포레이션 배면 직물을 지닌 치형 전동 벨트
JP2021507188A (ja) * 2017-12-13 2021-02-22 ゲイツ コーポレイション 背面帆布付き歯付き動力伝達ベルト
KR102429353B1 (ko) * 2017-12-13 2022-08-03 게이츠 코포레이션 배면 직물을 지닌 치형 전동 벨트
JP7197239B2 (ja) 2017-12-13 2022-12-27 ゲイツ コーポレイション 背面帆布付き歯付き動力伝達ベルト

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