US20010055667A1 - Processed fiber which is bondable to a rubber composition and a power transmission belt incorporating the processed fiber - Google Patents
Processed fiber which is bondable to a rubber composition and a power transmission belt incorporating the processed fiber Download PDFInfo
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- US20010055667A1 US20010055667A1 US09/114,848 US11484898A US2001055667A1 US 20010055667 A1 US20010055667 A1 US 20010055667A1 US 11484898 A US11484898 A US 11484898A US 2001055667 A1 US2001055667 A1 US 2001055667A1
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- Prior art keywords
- processing liquid
- fiber
- rubber
- power transmission
- transmission belt
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- 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
- B29D29/08—Toothed driving belts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
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- 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
- F16G1/28—Driving-belts with a contact surface of special shape, e.g. toothed
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- 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
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10S156/91—Bonding tire cord and elastomer: improved adhesive system
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/2457—Parallel ribs and/or grooves
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2971—Impregnation
Definitions
- This invention relates to fibers to be bonded to a rubber composition and, more particularly, to fibers that are treated to cause effective adherence of the fibers to a rubber composition.
- the invention is also directed to a power transmission belt with the treated fibers incorporated therein.
- JP-B Japanese Patent Publication
- JP-B Sho-60-24131 discloses treatment of fiber cords with an RFL liquid that includes a carboxyl group having acrylonitrile-butadiene rubber latex.
- JP-B Hei-6-41528 discloses treating cords with an epoxy compound or an isocyanate compound in a first step, treating the cords with an RFL liquid in a second step, and treating the cords with a rubber paste made from a rubber composition and a rubber chloride dissolved in a solvent in a third step.
- the adhesive composition consisting of an active compound, an RFL liquid, and an halogen-containing polymer has the drawback that use of the halogen-containing polymer must be limited to address environmental concerns.
- the invention is directed to processed fiber for bonding to a rubber composition.
- the processed fiber consists of unprocessed fiber treated with a) a first processing liquid having at least one of an isocyanate compound and an epoxy compound, b) a second processing liquid having RFL that includes at least one rubber latex selected from acrylonitrile-butadiene rubber latex and hydrogenated nitrile rubber latex, and c) a third processing liquid having rubber paste including acrylonitrile-butadiene rubber composition dissolved in a solvent and an isocyanate compound.
- the weight ratio of the isocyanate compound to the acrylonitrile-butadiene rubber composition is from 1/1 to 1/3.
- the third processing liquid has a solid content of from 3-7%.
- the fiber may be treated with the second processing liquid after being treated with the first processing liquid, with the fiber being treated with the third processing liquid after being treated with the second processing liquid.
- the fiber may be at least one of polyethylene terephthalate fiber (PET), polyethylene naphthalate fiber (PEN), aramid fiber, and 6-nylon.
- PET polyethylene terephthalate fiber
- PEN polyethylene naphthalate fiber
- aramid fiber aramid fiber
- 6-nylon 6-nylon
- the fiber may be treated with the first processing liquid for 0.5-30 seconds and thereafter heated at a temperature of 150-190° C. for from 2-5 minutes.
- the RFL processing liquid may be a mixture of resorcinol and formalin with rubber latex in which the molar ratio of resorcinol to formalin is from 3/1 to 1/3.
- the RFL processing liquid may be prepared by mixing a precondensate of resorcinol and formalin with rubber latex so that the resin content is from 5-100 parts by weight relative to 100 parts by weight of rubber content in the rubber latex and so that the solid content of the RFL processing liquid is from 5-40%.
- the fiber may be treated with the second processing liquid at 5-40° C. for 0.5-30 seconds and thereafter heated at a temperature of 220-250° C. for from 1-3 minutes.
- the fiber may be treated with the third processing liquid at 5-40° C. for 0.5-30 seconds and thereafter heated at a temperature of from 140-180° C. for from 3-7 minutes.
- the isocyanate compound in the first processing liquid may include one of 4,4′-diphenylmethane diisocyanate, toluene 2,4-diisocyanate, polymethylene polyphenyl-diisocynanate, hexamethylene diisocyanate, polyaryl polyisocyanate, and blocked polyisocyanate prepared by reacting an isocyanate compound with a blocking agent.
- the acrylonitrile-butadiene rubber composition in the third processing liquid may include acrylonitrile-butadiene rubber with at least one of a reinforcing agent, a filler, a softener, an anti-aging agent, and a vulcanization agent added thereto.
- the epoxy compound in the first processing liquid may include at least one of the reaction product of at least one of polyalcohol and polyalkylene glycol, a halogen-containing epoxy compound, and a reaction product of polyphenol.
- the epoxy compound in the first processing liquid may be mixed with an organic solvent.
- the invention is also directed to a power transmission belt having an endless body with a length and fiber embedded in the endless body, with the fiber having the composition as described above.
- the fiber may define a cord which extends lengthwise in the body.
- the body has a cushion layer made from rubber and the cord is embedded in the cushion layer and extends endlessly within the body.
- the compressible rubber may be made from alkylated chlorosulfonated polyethylene with a low density polyethylene that has a linear molecular structure and is chlorosulfonated to have a chlorine content of from 15-35% by weight and a sulfur content of from 0.5-2.5% by weight.
- the power transmission belt may be a V-belt or a V-ribbed belt.
- the power transmission belt may be a toothed belt having teeth spaced from each other lengthwise of the body, with the body having an inside layer in which the teeth are formed, and a back layer, with the cord being embedded in the back layer.
- the body has a compression section with rubber that includes at least one of alkylated chlorosulfonated polyethylene (ACSM), hydrogenated nitrile rubber (H-NBR), nitrile-butadiene rubber (NBR), chloroprene rubber (CR), and chlorosulfonated polyethylene rubber (CSM).
- ACSM alkylated chlorosulfonated polyethylene
- H-NBR hydrogenated nitrile rubber
- NBR nitrile-butadiene rubber
- CR chloroprene rubber
- CSM chlorosulfonated polyethylene rubber
- the body may have a cushion rubber layer in which the cord is embedded with the cushion rubber layer being made from a hydrogenated nitrile rubber composition.
- the hydrogenated rubber composition may include hydrogenated nitrile rubber to which is added at least one of a reinforcing agent, a filler, a softener, an anti-aging agent, a vulcanization promoter, and a vulcanizing agent.
- FIG. 1 is a cross-sectional view of a V-ribbed belt made according to the present invention.
- FIG. 2 is a fragmentary, side elevation view of a toothed belt, made according to the present invention.
- FIG. 3 is a cross-sectional view of V-belt, made according to the present invention.
- FIG. 4 is a graph showing the relationship between the weight ratio of isocyanate compound to acrylonitrile-butadiene rubber composition in processing liquid tested herein, with the liquid being controlled so as to all have a solid content of 5%, and the peeling force between rubber and fiber cords processed with the liquid;
- FIG. 5 is a graph showing the relationship between the solid content of the processing liquid tested herein, with the liquid being controlled so as to have a weight ratio of the isocyanate compound to acrylonitrile-butadiene rubber composition equal to one-half, and the peeling force between rubber and fiber cords processed with the liquid.
- the rubber composition used with the present invention consists essentially of hydrogenated nitrile rubber (H-NBR), hydrogenated nitrile rubber (H-NBR) with a metal salt of an unsaturated carboxylic acid added, alkylated chlorosulfonated polyethylene (ACSM), nitrile-butadiene rubber (NBR), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), or the like. These may contain a reinforcing agent such as carbon black, a filler, a softener, an anti-aging agent, a vulcanization promoter, and/or a vulcanizing agent such as sulfur, etc.
- H-NBR hydrogenated nitrile rubber
- H-NBR hydrogenated nitrile rubber
- CSM chlorosulfonated polyethylene rubber
- the hydrogenated nitrile rubber used herein has a degree of hydrogenation of not less than 80% and more preferably not less than 90% so as to exhibit good heat and ozone resistance.
- Hydrogenated nitrile rubber having a degree of hydrogenation less than 80% exhibits unsatisfactory heat resistance and ozone resistance.
- the amount of acrylonitrile bonded to the rubber is preferably from 20-45%.
- fibers suitable for use with the invention are polyethylene terephthalate fiber (PET), polyethylene naphthalate fiber (PEN), aramid fiber, 6-nylon, and the like.
- PET polyethylene terephthalate fiber
- PEN polyethylene naphthalate fiber
- aramid fiber 6-nylon, and the like.
- Polyethylene terephthalate fiber, polyethylene naphthalate fiber, and aramid fiber are preferred for their good heat resistance characteristics.
- the fiber may be used in any form, such as cords, woven fabrics, knitted fabrics, reed screens, etc.
- the fibers, processed/treated according to the present invention are also useful as reinforcing members in dynamic products such as conveyor belts, tires, etc.
- Fibers, according to the present invention, are processed/treated as described below.
- unprocessed fiber is dipped in a first processing liquid containing an isocyanate compound and/or an epoxy compound at room temperature for 0.5-30 seconds.
- the liquid is then dried while being passed through an oven maintained at a temperature of from 150-190° C. for 2-5 minutes.
- the fiber is treated with a second processing liquid of RFL that has at least one rubber latex selected from acrylonitrile-butadiene rubber latex (NBR latex) and hydrogenated nitrile rubber latex (H-NBR latex).
- the RFL liquid is prepared by mixing a precondensate of resorcinol and formalin with rubber latex, in which the molar ratio of resorcinol to formalin is preferably from 3/1 to 1/3 to improve the adhesion of the processed fiber.
- RFL liquid a precondensate of resorcinol and formalin is mixed with rubber latex so that its resin content is from 5-100 parts by weight relative to 100 parts by weight of the rubber content of the rubber latex.
- the overall solid content of the resulting RFL liquid is preferably from 5-40%.
- the temperature of the processing liquid is maintained between 5-40° C., with the fiber being dipped for from 0.5-30 seconds. After being dipped in the processing liquid, the fiber is dried while being passed through an oven maintained at a temperature from 220-250° C. for 1-3 minutes.
- the fiber is then treated with a third processing liquid having a rubber paste of an acrylonitrile-butadiene rubber composition dissolved in a solvent, and an isocyanate compound.
- the weight ratio of the isocyanate compound to the acrylonitrile-butadiene rubber composition is from 1/1 to 1/3.
- the third processing liquid preferably has a solid content of from 3-7%.
- the temperature of the processing liquid is between 5-40° C. with the fiber being dipped for from 0.5-30 seconds.
- the fiber is dried while being passed through an oven maintained at a temperature of from 140-180° C. for 3-7 minutes.
- the isocyanate compound in the first processing liquid may include, for example, 4,4′-diphenylmethane diisocyanate, toluene 2,4-diisocyanate, polymethylene polyphenyl-diisocynanate, hexamethylene diisocyanate, polyaryl polyisocyanate (such as that sold commercially under the trademark PAPITM), etc.
- the isocyanate compound is used after being mixed with an organic solvent, such as toluene, methyl ethyl ketone, etc.
- blocked polyisocyanates prepared by reacting an isocyanate compound, such as those mentioned above, with a blocking agent, such as phenols, tertiary alcohols, secondary alcohols, etc., to block the isocyanate groups of the polyisocyanate.
- a blocking agent such as phenols, tertiary alcohols, secondary alcohols, etc.
- Examples of epoxy compound in the first processing liquid are reaction products of polyalcohol such as ethylene glycol, glycerin, pentaerythritol, and the like, or polyalkylene-glycols such as polyethylene glycol and the like, with halogen-containing epoxy compounds such as epichlorohydrin, reaction products of polyphenols such as resorcinol, bis(4-hydroxyphenyl)dimethylmethane, phenol-formaldehyde resin, resorcinol-formaldehyde resin, and the like, with halogen-containing epoxy compounds, etc.
- the epoxy compound is used after being mixed with an organic solvent such as toluene, methyl ethyl ketone, etc.
- the RFL liquid in the second processing liquid may be prepared by mixing a precondensate of resorcinol and formalin with at least one rubber latex selected from nitrile rubber latex and hydrogenated nitrile rubber latex.
- the molar ratio of resorcinol to formalin is preferably from 3/1 to 1/3 to improve adhesion of the fiber processed therewith.
- the precondensate of resorcinol and formalin is mixed with rubber latex so that its resin content is from 5-100 parts by weight relative to 100 parts by weight of the rubber content of the rubber latex.
- the overall solid content of the resulting RFL liquid is from 5-40%.
- the third processing liquid may include rubber paste made from acrylonitrile-butadiene rubber composition dissolved in a solvent and an isocyanate compound.
- the ratio of the weight of the isocyanate compound to the acrylonitrile-butadiene rubber composition is from 1/1 to 1/3.
- the solid content is from 3-7%.
- the weight ratio is larger than 1/1, the pot stability of the processing liquid is not adequate so that the liquid is often solidified during the performance of the fiber processing steps. On the other hand, if the weight ratio is smaller than 1/3, adhesion of the processed fiber may not be adequate. If the solid content of the liquid is smaller than 3% or larger than 7%, the adhesive qualities of the processed fiber may not be adequate.
- the solid content of the processing liquid may be measured as follows. A sample of the processing liquid is put into a metering bottle and its mass (W 1 ) determined. The processing liquid is then put into an oven and dried until the mass of the sample becomes constant. The final mass (W 2 ) of the sample is determined. The solid content is calculated by the following formula: W 2 /W 1 ⁇ 100(%).
- the acrylonitrile-butadiene rubber composition to be used herein may be any ordinary one prepared by adding to acrylonitrile-butadiene rubber a reinforcing agent such as carbon black, a filler, a softener, an anti-aging agent, a vulcanization promoter, and/or a vulcanizing agent such as sulfur, etc.
- a reinforcing agent such as carbon black
- a filler such as carbon black
- a softener such as an anti-aging agent
- a vulcanization promoter such as sulfur, etc.
- a V-ribbed belt is shown at 10 as one potential environment for fibers, treated/processed according to the present invention.
- the V-ribbed belt 10 has a body 12 with an inside layer 14 and a back layer 16 .
- the body 12 has a cushion rubber layer 18 in which laterally spaced load carrying cords 20 are embedded.
- the load carrying cords 20 extend lengthwise of the belt body 12 in an endless path.
- Grooves 22 are formed through the inside body layer 14 to define laterally spaced, V-shaped ribs 24 .
- the ribs 24 are formed in a compression section 26 , which in FIG. 2 resides below a neutral axis defined by the load carrying cords 20 .
- the backside surface 28 is covered by, in this case, two layers of rubber-impregnated canvas cloth 30 .
- the compression section 26 of the belt body 12 is reinforced by discrete, laterally extending, short fibers 32 .
- the load carrying cords 20 are made with fibers processed according to the present invention.
- the load carrying cords 20 are constructed to exhibit high strength and low elongation.
- the fibers 34 defining the cords 20 are polyethylene terephthalate fiber (PET), polyethylene naphthalate fiber (PEN), or aramid fiber.
- the compression section 26 is made from a compressible rubber layer including alkylated chlorosulfonated polyethylene (ACSM), hydrogenated nitrile rubber (H-NBR), nitrile butadiene rubber (NBR), chloroprene rubber (CR), and chlorosulfonated polyethylene rubber (CSM), which exhibit good resistance to thermal deterioration.
- ACSM alkylated chlorosulfonated polyethylene
- H-NBR hydrogenated nitrile rubber
- NBR nitrile butadiene rubber
- CR chloroprene rubber
- CSM chlorosulfonated polyethylene rubber
- the alkylated chlorosulfonated polyethylene is a low density polyethylene having a linear molecular structure which is chlorosulfonated to have a chlorine content of from 15-35% by weight and a sulfur content of from 0.5-2.5% by weight.
- the fibers 32 may be made from nylon 6, nylon 66, polyester, cotton, or aramid.
- the fibers 32 resist lateral deformation of the belt body 12 .
- friction between the surfaces 36 , 38 and a cooperating pulley (not shown) which contacts the surfaces 36 , 38 is reduced to thereby account for noise reduction during operation.
- Aramid fibers are preferred because of their stiffness, high strength, and abrasion resistance.
- the short aramid fibers 32 preferably have a length of from 1-20 mm and are present in an amount from 1-30 parts by weight per 100 parts by weight of rubber.
- Aramid fibers having aromatic rings in the molecular structure are preferred. This type of aramid fiber is available and sold commercially under the trademarks CONEXTM, NOMEXTM, KEVLARTM, TECHNORATM and TWARONTM.
- the amount of short aramid fibers is less than 1 part by weight, the rubber in the compression section 26 may become excessively sticky and thus prone to wearing. On the other hand, if the aramid fibers are present in an amount greater than 30 parts by weight, the fibers 32 may not uniformly disperse in the rubber in the compression section 26 .
- the fibers 34 are preferably aramid fibers having an aromatic ring in the main chain of the molecular structure. Fibers suitable for this purpose are currently available commercially and sold under the trademarks KEVLARTM, TECHNORATM and TWARONTM.
- the load carrying cords 20 may be formed by gathering 2-5 non-twisted bundles each having an overall thickness of from 300-3100 denier. Each bundle has 100-3000 monofilaments each having a thickness of from 1-3 denier. The bundles are final twisted at a count of 4-50 twists per 10 cm.
- the fiber bundles may be subjected to primary and final twisting.
- primary twisting may make it difficult for RFL liquid to penetrate into the depth of the cords 20 .
- the cushion rubber layer 18 may be made from a hydrogenated nitrile rubber composition prepared by adding to ordinary hydrogenated nitrile rubber a reinforcing agent such as carbon black, a filler, a softener, an anti-aging agent, a vulcanization promoter, and/or a vulcanizing agents, such as sulfur, etc.
- a reinforcing agent such as carbon black
- a filler such as carbon black
- a softener such as carbon black
- an anti-aging agent such as sulfur
- a vulcanization promoter such as sulfur, etc.
- the load carrying cords 20 can be used in other belts, such as the toothed belt, as shown at 40 in FIG. 2.
- the toothed belt 40 in FIG. 2 has a body 42 with teeth 44 formed therein and spaced lengthwise from each other, i.e. in the direction of the double-headed arrow L.
- the belt body 42 has a back side layer 46 having load carrying cords 48 , made according to the present invention, incorporated therein.
- the teeth 44 are covered with a canvas layer 50 .
- FIG. 3 the invention is shown incorporated into a V-belt 52 having a body 54 with exposed, pulley-engaging side surfaces 56 , 58 .
- the body 54 defines a compression section 60 with short, reinforcing fibers 62 embedded therein.
- the body 54 has a cushion rubber layer 64 with load carrying cords 66 , according to the present invention, embedded therein and extending lengthwise of the belt body 54 in an endless path.
- a rubber-impregnated canvas cloth layer 68 is applied over the inside surface 70 of the compression section 60 .
- Three such layers 68 are applied to the outside surface 72 of the cushion rubber layer 64 .
- the first processing liquid was prepared by combining and thoroughly mixing 10 parts by weight of PAPI-135 (polyisocyanate compound manufactured by Mitsubishi Chemical Daw Co.) and 90 parts by weight of toluene. TABLE 1 Chemicals Amount (wt. pts.) PAPI-135 (*1) 10 Toluene 90 Total 100
- a third processing liquid which was an adhesive, nitrile rubber composition, as set out in Table 3 below, was prepared. TABLE 3 Chemicals Amount (wt. pts.) NBR 100 Zinc Flower 5 Stearic Acid 1 Carbon Black 15 Silicic Acid Hydrate 30 Resorcinol-Formalin Polymer 2 Promoter (MBTS) 1.5 Sulfur 2 Hexamethylol-melamine 4 Total 160.5
- the fiber cords were processed with the processing liquids prepared above and the resulting processed fiber cords were tested for adhesion to a hydrogenated nitrile rubber composition, as set forth below.
- the processed fiber cords were incorporated into V-ribbed belts, which were subjected to the running tests as further described below.
- Cords of polyethylene teraphthalate fiber were formed using 5 bundles of 1100 denier each, and twisted at a primary twist count of 29/10 cm and a final twist count of 13/10 cm.
- the cords were dipped in the first processing liquid prepared above and heated at 180° C. for 5 minutes.
- the cords were then dipped in the second processing liquid, heated at 230° C. for 2 minutes, and finally dipped in the third processing liquid and dried at 160° for 5 minutes.
- a cord processor was used for this treatment.
- a plurality of the processed cords were densely aligned, side-to-side, to produce an overall width of 25 mm and pressed against the hydrogenated nitrile rubber composition at a temperature of 150° C. and a pressure of 2 kPa for 30 minutes to prepare a sheet sample having a 25 mm width, a length of 140 mm, and a thickness of 4 mm.
- the peeling force of the samples was measured at room temperature and at 100° C.
- the test sample was thermally cured at 120° C. for 8 days and subjected to the same tensile test at room temperature. The data obtained from this testing is shown in Table 6, below, and in FIGS. 3 and 4.
- the canvas was wound around a cylindrical mold to form a one ply canvas layer.
- the processed fiber cord of Example 2 was then wrapped around the mold, followed by a rubber sheet of ACSM rubber having a composition shown in Table 6.
- the resulting belt sleeve was vulcanized in a conventional manner at 160° C. for 30 minutes.
- the vulcanized rubber sleeve was trained around spaced driving and driven rolls in a grinding assembly and rotated therearound under tension.
- a grinding wheel having 150 mesh diamond on its surface was pressed against the sleeve while being rotated at 1600 rpm to thereby form ribs thereon.
- the ribbed sleeve was removed from the grinding assembly and cut into belts of predetermined width as the sleeve was rotated.
- the resulting belts were K-type 3-ribbed belts having a length of 1100 mm according to the RMA Standard.
- the belts had a rib pitch of 3.56 mm, a rib height of 2.9 mm, and a rib angle of 40°.
- V-ribbed belts were set in a triaxial pulley system having a driving pulley and a driven pulley each with a 120 mm diameter, and a tensioning pulley having a 45 mm diameter. A tension of 830 N was imparted to the belt through the tensioning pulley. The belt was run at an ambient temperature of 85° C. with the driving pulley rotated at 4900 rpm with a load of 12 PS applied to the driven pulley.
- the running tests verify that when the ratio by weight of the isocyanate compound to the acrylonitrile-butadiene rubber composition in the third processing liquid used falls between 1/1 and 1/3, and when the solid content of the third processing liquid falls between 3 and 7%, the peeling force between the fiber cords and the adhesive rubber layer in the belts is high. At the same time, the adhesive-processed cords remain flexible, with the result being that the life of the belts is long.
- the present invention makes possible the manufacture of an adhesive-processed fiber having good adhesion without requiring use of a halogen containing polymer.
- the fiber used in load carrying cords in a power transmission belt long belt life may result, even with the belt operating in a high temperature environment.
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Abstract
Processed fiber for bonding to a rubber composition. The processed fiber consists of unprocessed fiber treated with a) a first processing liquid having at least one of an isocyanate compound and an epoxy compound, b) a second processing liquid having RFL that includes at least one rubber latex selected from acrylonitrile-butadiene rubber latex and hydrogenated nitrile rubber latex, and c) a third processing liquid having rubber paste including acrylonitrile-butadiene rubber composition dissolved in a solvent and an isocyanate compound. The weight ratio of the isocyanate compound to the acrylonitrile-butadiene rubber composition is from 1/1 to 1/3. The third processing liquid has a solid content of from 3-7%.
Description
- 1. Field of the Invention
- This invention relates to fibers to be bonded to a rubber composition and, more particularly, to fibers that are treated to cause effective adherence of the fibers to a rubber composition. The invention is also directed to a power transmission belt with the treated fibers incorporated therein.
- 2. Background Art
- There has been an ongoing trend to design and produce energy-efficient automobiles. Typically, this efficiency is attributable to the compaction of these cars which is made possible, in part, by a reduction in the size of the engine compartments. This often results in a higher temperature environment in the compartments. As a result, power transmission belts used in the automobiles are often subjected to high operating temperatures.
- Conventional power transmission belts are commonly made from natural rubber, styrene-butadiene rubber, and chloroprene rubber. The compression sections of the belts are prone to cracking at these high temperatures at a relatively early stage in the intended belt life.
- Recently, hydrogenated nitrile rubbers have been developed as a heat-resistant polymer for use in power transmission belts, including V-belts, V-ribbed belts and toothed belts. A rubber composition with hydrogenated nitrile rubber and a metal salt of an unsaturated carboxylic acid has also been used in an elastic portion of the power transmission belts. Efforts are ongoing to improve the adhesion of fiber, load carrying cords to hydrogenated nitrile rubber.
- As an example, Japanese Patent Publication (JP-B)Sho-60-24131 discloses treatment of fiber cords with an RFL liquid that includes a carboxyl group having acrylonitrile-butadiene rubber latex.
- JP-B Hei-6-41528 discloses treating cords with an epoxy compound or an isocyanate compound in a first step, treating the cords with an RFL liquid in a second step, and treating the cords with a rubber paste made from a rubber composition and a rubber chloride dissolved in a solvent in a third step.
- Treating fiber cords with an RFL liquid that includes a carboxyl group having acrylonitrile-butadiene rubber latex improves adhesion of the fiber cords to hydrogenated nitrile rubber. However, it has been found through testing that, when power transmission belts incorporating the process cords are repeatedly fatigued during operation, the cords tend to peel off from the adhesion rubber layer at the interface therebetween at an early stage, demonstrating that the adhesion between the cords and rubber is unsatisfactory.
- The adhesive composition consisting of an active compound, an RFL liquid, and an halogen-containing polymer has the drawback that use of the halogen-containing polymer must be limited to address environmental concerns.
- The method described in JP-B Hei-6-41528 also has the drawback that the use of rubber chloride must be limited for environmental reasons. Further, the availability of this composition in the future is uncertain.
- In one form, the invention is directed to processed fiber for bonding to a rubber composition. The processed fiber consists of unprocessed fiber treated with a) a first processing liquid having at least one of an isocyanate compound and an epoxy compound, b) a second processing liquid having RFL that includes at least one rubber latex selected from acrylonitrile-butadiene rubber latex and hydrogenated nitrile rubber latex, and c) a third processing liquid having rubber paste including acrylonitrile-butadiene rubber composition dissolved in a solvent and an isocyanate compound. The weight ratio of the isocyanate compound to the acrylonitrile-butadiene rubber composition is from 1/1 to 1/3. The third processing liquid has a solid content of from 3-7%.
- The fiber may be treated with the second processing liquid after being treated with the first processing liquid, with the fiber being treated with the third processing liquid after being treated with the second processing liquid.
- The fiber may be at least one of polyethylene terephthalate fiber (PET), polyethylene naphthalate fiber (PEN), aramid fiber, and 6-nylon.
- The fiber may be treated with the first processing liquid for 0.5-30 seconds and thereafter heated at a temperature of 150-190° C. for from 2-5 minutes.
- The RFL processing liquid may be a mixture of resorcinol and formalin with rubber latex in which the molar ratio of resorcinol to formalin is from 3/1 to 1/3.
- The RFL processing liquid may be prepared by mixing a precondensate of resorcinol and formalin with rubber latex so that the resin content is from 5-100 parts by weight relative to 100 parts by weight of rubber content in the rubber latex and so that the solid content of the RFL processing liquid is from 5-40%.
- The fiber may be treated with the second processing liquid at 5-40° C. for 0.5-30 seconds and thereafter heated at a temperature of 220-250° C. for from 1-3 minutes.
- The fiber may be treated with the third processing liquid at 5-40° C. for 0.5-30 seconds and thereafter heated at a temperature of from 140-180° C. for from 3-7 minutes.
- The isocyanate compound in the first processing liquid may include one of 4,4′-diphenylmethane diisocyanate, toluene 2,4-diisocyanate, polymethylene polyphenyl-diisocynanate, hexamethylene diisocyanate, polyaryl polyisocyanate, and blocked polyisocyanate prepared by reacting an isocyanate compound with a blocking agent.
- The acrylonitrile-butadiene rubber composition in the third processing liquid may include acrylonitrile-butadiene rubber with at least one of a reinforcing agent, a filler, a softener, an anti-aging agent, and a vulcanization agent added thereto.
- The epoxy compound in the first processing liquid may include at least one of the reaction product of at least one of polyalcohol and polyalkylene glycol, a halogen-containing epoxy compound, and a reaction product of polyphenol.
- The epoxy compound in the first processing liquid may be mixed with an organic solvent.
- The invention is also directed to a power transmission belt having an endless body with a length and fiber embedded in the endless body, with the fiber having the composition as described above.
- The fiber may define a cord which extends lengthwise in the body.
- In one form, the body has a cushion layer made from rubber and the cord is embedded in the cushion layer and extends endlessly within the body.
- The compressible rubber may be made from alkylated chlorosulfonated polyethylene with a low density polyethylene that has a linear molecular structure and is chlorosulfonated to have a chlorine content of from 15-35% by weight and a sulfur content of from 0.5-2.5% by weight.
- The power transmission belt may be a V-belt or a V-ribbed belt.
- The power transmission belt may be a toothed belt having teeth spaced from each other lengthwise of the body, with the body having an inside layer in which the teeth are formed, and a back layer, with the cord being embedded in the back layer.
- In one form, the body has a compression section with rubber that includes at least one of alkylated chlorosulfonated polyethylene (ACSM), hydrogenated nitrile rubber (H-NBR), nitrile-butadiene rubber (NBR), chloroprene rubber (CR), and chlorosulfonated polyethylene rubber (CSM).
- The body may have a cushion rubber layer in which the cord is embedded with the cushion rubber layer being made from a hydrogenated nitrile rubber composition.
- The hydrogenated rubber composition may include hydrogenated nitrile rubber to which is added at least one of a reinforcing agent, a filler, a softener, an anti-aging agent, a vulcanization promoter, and a vulcanizing agent.
- FIG. 1 is a cross-sectional view of a V-ribbed belt made according to the present invention;
- FIG. 2 is a fragmentary, side elevation view of a toothed belt, made according to the present invention;
- FIG. 3 is a cross-sectional view of V-belt, made according to the present invention;
- FIG. 4 is a graph showing the relationship between the weight ratio of isocyanate compound to acrylonitrile-butadiene rubber composition in processing liquid tested herein, with the liquid being controlled so as to all have a solid content of 5%, and the peeling force between rubber and fiber cords processed with the liquid; and
- FIG. 5 is a graph showing the relationship between the solid content of the processing liquid tested herein, with the liquid being controlled so as to have a weight ratio of the isocyanate compound to acrylonitrile-butadiene rubber composition equal to one-half, and the peeling force between rubber and fiber cords processed with the liquid.
- The rubber composition used with the present invention consists essentially of hydrogenated nitrile rubber (H-NBR), hydrogenated nitrile rubber (H-NBR) with a metal salt of an unsaturated carboxylic acid added, alkylated chlorosulfonated polyethylene (ACSM), nitrile-butadiene rubber (NBR), chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), or the like. These may contain a reinforcing agent such as carbon black, a filler, a softener, an anti-aging agent, a vulcanization promoter, and/or a vulcanizing agent such as sulfur, etc. The hydrogenated nitrile rubber composition is preferred.
- In a preferred form, the hydrogenated nitrile rubber used herein has a degree of hydrogenation of not less than 80% and more preferably not less than 90% so as to exhibit good heat and ozone resistance. Hydrogenated nitrile rubber having a degree of hydrogenation less than 80% exhibits unsatisfactory heat resistance and ozone resistance. For purposes of oil and cold resistance, the amount of acrylonitrile bonded to the rubber is preferably from 20-45%.
- Examples of fibers suitable for use with the invention are polyethylene terephthalate fiber (PET), polyethylene naphthalate fiber (PEN), aramid fiber, 6-nylon, and the like. Polyethylene terephthalate fiber, polyethylene naphthalate fiber, and aramid fiber are preferred for their good heat resistance characteristics.
- The fiber may be used in any form, such as cords, woven fabrics, knitted fabrics, reed screens, etc. The fibers, processed/treated according to the present invention, are also useful as reinforcing members in dynamic products such as conveyor belts, tires, etc.
- Fibers, according to the present invention, are processed/treated as described below.
- First, unprocessed fiber is dipped in a first processing liquid containing an isocyanate compound and/or an epoxy compound at room temperature for 0.5-30 seconds. The liquid is then dried while being passed through an oven maintained at a temperature of from 150-190° C. for 2-5 minutes.
- Next, the fiber is treated with a second processing liquid of RFL that has at least one rubber latex selected from acrylonitrile-butadiene rubber latex (NBR latex) and hydrogenated nitrile rubber latex (H-NBR latex). The RFL liquid is prepared by mixing a precondensate of resorcinol and formalin with rubber latex, in which the molar ratio of resorcinol to formalin is preferably from 3/1 to 1/3 to improve the adhesion of the processed fiber.
- To prepare the RFL liquid, a precondensate of resorcinol and formalin is mixed with rubber latex so that its resin content is from 5-100 parts by weight relative to 100 parts by weight of the rubber content of the rubber latex. The overall solid content of the resulting RFL liquid is preferably from 5-40%.
- The temperature of the processing liquid is maintained between 5-40° C., with the fiber being dipped for from 0.5-30 seconds. After being dipped in the processing liquid, the fiber is dried while being passed through an oven maintained at a temperature from 220-250° C. for 1-3 minutes.
- The fiber is then treated with a third processing liquid having a rubber paste of an acrylonitrile-butadiene rubber composition dissolved in a solvent, and an isocyanate compound. The weight ratio of the isocyanate compound to the acrylonitrile-butadiene rubber composition is from 1/1 to 1/3. The third processing liquid preferably has a solid content of from 3-7%.
- During this step, the temperature of the processing liquid is between 5-40° C. with the fiber being dipped for from 0.5-30 seconds. After the fiber is dipped in the third processing liquid, the fiber is dried while being passed through an oven maintained at a temperature of from 140-180° C. for 3-7 minutes.
- The isocyanate compound in the first processing liquid may include, for example, 4,4′-diphenylmethane diisocyanate, toluene 2,4-diisocyanate, polymethylene polyphenyl-diisocynanate, hexamethylene diisocyanate, polyaryl polyisocyanate (such as that sold commercially under the trademark PAPI™), etc. The isocyanate compound is used after being mixed with an organic solvent, such as toluene, methyl ethyl ketone, etc.
- Also useable are blocked polyisocyanates prepared by reacting an isocyanate compound, such as those mentioned above, with a blocking agent, such as phenols, tertiary alcohols, secondary alcohols, etc., to block the isocyanate groups of the polyisocyanate.
- Examples of epoxy compound in the first processing liquid are reaction products of polyalcohol such as ethylene glycol, glycerin, pentaerythritol, and the like, or polyalkylene-glycols such as polyethylene glycol and the like, with halogen-containing epoxy compounds such as epichlorohydrin, reaction products of polyphenols such as resorcinol, bis(4-hydroxyphenyl)dimethylmethane, phenol-formaldehyde resin, resorcinol-formaldehyde resin, and the like, with halogen-containing epoxy compounds, etc. The epoxy compound is used after being mixed with an organic solvent such as toluene, methyl ethyl ketone, etc.
- The RFL liquid in the second processing liquid may be prepared by mixing a precondensate of resorcinol and formalin with at least one rubber latex selected from nitrile rubber latex and hydrogenated nitrile rubber latex. The molar ratio of resorcinol to formalin is preferably from 3/1 to 1/3 to improve adhesion of the fiber processed therewith. The precondensate of resorcinol and formalin is mixed with rubber latex so that its resin content is from 5-100 parts by weight relative to 100 parts by weight of the rubber content of the rubber latex. The overall solid content of the resulting RFL liquid is from 5-40%.
- The third processing liquid may include rubber paste made from acrylonitrile-butadiene rubber composition dissolved in a solvent and an isocyanate compound. The ratio of the weight of the isocyanate compound to the acrylonitrile-butadiene rubber composition is from 1/1 to 1/3. The solid content is from 3-7%.
- If the weight ratio is larger than 1/1, the pot stability of the processing liquid is not adequate so that the liquid is often solidified during the performance of the fiber processing steps. On the other hand, if the weight ratio is smaller than 1/3, adhesion of the processed fiber may not be adequate. If the solid content of the liquid is smaller than 3% or larger than 7%, the adhesive qualities of the processed fiber may not be adequate.
- The solid content of the processing liquid may be measured as follows. A sample of the processing liquid is put into a metering bottle and its mass (W1) determined. The processing liquid is then put into an oven and dried until the mass of the sample becomes constant. The final mass (W2) of the sample is determined. The solid content is calculated by the following formula: W2/W1×100(%).
- The acrylonitrile-butadiene rubber composition to be used herein may be any ordinary one prepared by adding to acrylonitrile-butadiene rubber a reinforcing agent such as carbon black, a filler, a softener, an anti-aging agent, a vulcanization promoter, and/or a vulcanizing agent such as sulfur, etc.
- In FIG. 1, a V-ribbed belt is shown at10 as one potential environment for fibers, treated/processed according to the present invention. The V-ribbed
belt 10 has a body 12 with aninside layer 14 and aback layer 16. The body 12 has acushion rubber layer 18 in which laterally spacedload carrying cords 20 are embedded. Theload carrying cords 20 extend lengthwise of the belt body 12 in an endless path.Grooves 22 are formed through theinside body layer 14 to define laterally spaced, V-shapedribs 24. Theribs 24 are formed in acompression section 26, which in FIG. 2 resides below a neutral axis defined by theload carrying cords 20. Thebackside surface 28 is covered by, in this case, two layers of rubber-impregnatedcanvas cloth 30. Thecompression section 26 of the belt body 12 is reinforced by discrete, laterally extending,short fibers 32. - In this embodiment, the
load carrying cords 20 are made with fibers processed according to the present invention. Theload carrying cords 20 are constructed to exhibit high strength and low elongation. In this embodiment, thefibers 34 defining thecords 20 are polyethylene terephthalate fiber (PET), polyethylene naphthalate fiber (PEN), or aramid fiber. - The
compression section 26 is made from a compressible rubber layer including alkylated chlorosulfonated polyethylene (ACSM), hydrogenated nitrile rubber (H-NBR), nitrile butadiene rubber (NBR), chloroprene rubber (CR), and chlorosulfonated polyethylene rubber (CSM), which exhibit good resistance to thermal deterioration. - The alkylated chlorosulfonated polyethylene is a low density polyethylene having a linear molecular structure which is chlorosulfonated to have a chlorine content of from 15-35% by weight and a sulfur content of from 0.5-2.5% by weight.
- The
fibers 32 may be made from nylon 6,nylon 66, polyester, cotton, or aramid. Thefibers 32 resist lateral deformation of the belt body 12. By exposing thefibers 32 at the side surfaces 36, 38 of theribs 24, friction between thesurfaces surfaces - For maximum effect, the
short aramid fibers 32 preferably have a length of from 1-20 mm and are present in an amount from 1-30 parts by weight per 100 parts by weight of rubber. Aramid fibers having aromatic rings in the molecular structure are preferred. This type of aramid fiber is available and sold commercially under the trademarks CONEX™, NOMEX™, KEVLAR™, TECHNORA™ and TWARON™. - If the amount of short aramid fibers is less than 1 part by weight, the rubber in the
compression section 26 may become excessively sticky and thus prone to wearing. On the other hand, if the aramid fibers are present in an amount greater than 30 parts by weight, thefibers 32 may not uniformly disperse in the rubber in thecompression section 26. - In the
load carrying cords 20, thefibers 34 are preferably aramid fibers having an aromatic ring in the main chain of the molecular structure. Fibers suitable for this purpose are currently available commercially and sold under the trademarks KEVLAR™, TECHNORA™ and TWARON™. - The
load carrying cords 20 may be formed by gathering 2-5 non-twisted bundles each having an overall thickness of from 300-3100 denier. Each bundle has 100-3000 monofilaments each having a thickness of from 1-3 denier. The bundles are final twisted at a count of 4-50 twists per 10 cm. - The fiber bundles may be subjected to primary and final twisting. However, primary twisting may make it difficult for RFL liquid to penetrate into the depth of the
cords 20. - The
cushion rubber layer 18 may be made from a hydrogenated nitrile rubber composition prepared by adding to ordinary hydrogenated nitrile rubber a reinforcing agent such as carbon black, a filler, a softener, an anti-aging agent, a vulcanization promoter, and/or a vulcanizing agents, such as sulfur, etc. - The
load carrying cords 20, as processed according to the present invention, can be used in other belts, such as the toothed belt, as shown at 40 in FIG. 2. Thetoothed belt 40 in FIG. 2 has abody 42 withteeth 44 formed therein and spaced lengthwise from each other, i.e. in the direction of the double-headed arrow L. Thebelt body 42 has aback side layer 46 havingload carrying cords 48, made according to the present invention, incorporated therein. Theteeth 44 are covered with acanvas layer 50. - In FIG. 3, the invention is shown incorporated into a V-
belt 52 having abody 54 with exposed, pulley-engaging side surfaces 56, 58. Thebody 54 defines acompression section 60 with short, reinforcingfibers 62 embedded therein. Thebody 54 has acushion rubber layer 64 withload carrying cords 66, according to the present invention, embedded therein and extending lengthwise of thebelt body 54 in an endless path. A rubber-impregnatedcanvas cloth layer 68 is applied over theinside surface 70 of thecompression section 60. Threesuch layers 68 are applied to theoutside surface 72 of thecushion rubber layer 64. - Further examples of the present invention are described below and compared to conventional belt samples.
- The first processing liquid was prepared by combining and thoroughly mixing 10 parts by weight of PAPI-135 (polyisocyanate compound manufactured by Mitsubishi Chemical Daw Co.) and 90 parts by weight of toluene.
TABLE 1 Chemicals Amount (wt. pts.) PAPI-135 (*1) 10 Toluene 90 Total 100 - A second processing liquid as in Table 2, below, was prepared.
TABLE 2 Chemicals Amount (wt. pts.) Resorcinol 11.0 37% Formalin 16.2 Sodium Hydroxide (10%) 3.0 Water 235.8 NBR Latex (40%) 250.0 Ammonium Hydroxide 11.3 Water 59.2 Total 586.5 - 11.0 parts by weight of resorcinol, 16.2 parts by weight of 37% formalin, and 3.0 parts by weight of an aqueous solution of 10% sodium hydroxide were added to 235.8 parts by weight of water. The components were fully mixed and cured at 25° C. for six hours.
- In a separate operation, 59.2 parts by weight of water were added to 100 parts by weight of NBR latex (rubber content: 40%) and mixed. This mixture was then added to the resorcinol-formalin reaction liquid prepared above while the mixture was being gradually stirred, until a uniform state was achieved. The mixture was then cured at 25° C. for 20 hours to obtain the second processing liquid.
- A third processing liquid which was an adhesive, nitrile rubber composition, as set out in Table 3 below, was prepared.
TABLE 3 Chemicals Amount (wt. pts.) NBR 100 Zinc Flower 5 Stearic Acid 1 Carbon Black 15 Silicic Acid Hydrate 30 Resorcinol-Formalin Polymer 2 Promoter (MBTS) 1.5 Sulfur 2 Hexamethylol-melamine 4 Total 160.5 - All chemicals except sulfur were mixed in a BP model Banbury mixer in a preliminary step. The resulting mixture was formed into non-vulcanized rubber sheets using a laboratory roller to which sulfur was added. The resulting composition was then dissolved in toluene to prepare rubber paste having a solid content of from 1 to 9%. An isocyanate compound (PAPI-135) was added to this rubber paste. The ratio by weight of the isocyanate compound to the nitrile rubber composition was from 1/4 to 2/1. Ten types of the third processing liquid were thus prepared, as described in Table 4, below.
TABLE 4 Inventive Comparative Examples Samples 1 2 3 1 2 Solid Content (%) 3 5 7 1 9 Isocyanate Compound Rubber 1/2 1/2 1/2 1/2 1/2 Composition (ratio by weight) Inventive Comparative Examples Samples 4 5 3 4 Solid Content (%) 5 5 5 5 Isocyanate Compound/ Rubber 1/1 1/3 2/1 1/4 Composition (ratio by weight) - The fiber cords were processed with the processing liquids prepared above and the resulting processed fiber cords were tested for adhesion to a hydrogenated nitrile rubber composition, as set forth below. The processed fiber cords were incorporated into V-ribbed belts, which were subjected to the running tests as further described below.
- Cords of polyethylene teraphthalate fiber were formed using 5 bundles of 1100 denier each, and twisted at a primary twist count of 29/10 cm and a final twist count of 13/10 cm. The cords were dipped in the first processing liquid prepared above and heated at 180° C. for 5 minutes. The cords were then dipped in the second processing liquid, heated at 230° C. for 2 minutes, and finally dipped in the third processing liquid and dried at 160° for 5 minutes. For this treatment, a cord processor was used.
- The processed cords were subjected to testing for adhesion to the hydrogenated nitrile rubber composition as shown in Table 5, below, to measure the force required to peel the cords from the rubber.
TABLE 5 Chemicals Amount (wt. pts.) H-NBR 100 Zinc Flower 5 Stearic Acid 1 Carbon Black 25 Silicic Acid Hydrate 20 Resorcinol-Formalin Polymer 2 Anti-aging Agent 2 Promoter (MBTS) 1 Promoter (CM) 1 Hexamethylol-melamine 2 Sulfur 1 Total 160 - A plurality of the processed cords were densely aligned, side-to-side, to produce an overall width of 25 mm and pressed against the hydrogenated nitrile rubber composition at a temperature of 150° C. and a pressure of 2 kPa for 30 minutes to prepare a sheet sample having a 25 mm width, a length of 140 mm, and a thickness of 4 mm. Using a tensile tester, the peeling force of the samples was measured at room temperature and at 100° C. In addition, the test sample was thermally cured at 120° C. for 8 days and subjected to the same tensile test at room temperature. The data obtained from this testing is shown in Table 6, below, and in FIGS. 3 and 4.
TABLE 6 Chemicals Amount (wt. pts.) ACSM 100 Stearic Acid 1 Magnesium Oxide- Aluminum Oxide 10 Nickel Dibutylthiocarbamate 2 Processed Oil 8 Carbon Black 36 Chopped Yarns of Aramid 10 Chopped Yams of Nylon 10 Promoter (MBTS) 0.5 Promoter (DPTT) 2 - A sheet of plain weave fabric, having cotton warp and weft yarns, was impregnated with hydrogenated nitrile rubber having a composition shown in Table 5, through friction coating. The canvas was wound around a cylindrical mold to form a one ply canvas layer. The processed fiber cord of Example 2 was then wrapped around the mold, followed by a rubber sheet of ACSM rubber having a composition shown in Table 6. The resulting belt sleeve was vulcanized in a conventional manner at 160° C. for 30 minutes.
- The vulcanized rubber sleeve was trained around spaced driving and driven rolls in a grinding assembly and rotated therearound under tension. A grinding wheel having 150 mesh diamond on its surface was pressed against the sleeve while being rotated at 1600 rpm to thereby form ribs thereon. The ribbed sleeve was removed from the grinding assembly and cut into belts of predetermined width as the sleeve was rotated. The resulting belts were K-type 3-ribbed belts having a length of 1100 mm according to the RMA Standard. The belts had a rib pitch of 3.56 mm, a rib height of 2.9 mm, and a rib angle of 40°.
- The V-ribbed belts were set in a triaxial pulley system having a driving pulley and a driven pulley each with a 120 mm diameter, and a tensioning pulley having a 45 mm diameter. A tension of 830 N was imparted to the belt through the tensioning pulley. The belt was run at an ambient temperature of 85° C. with the driving pulley rotated at 4900 rpm with a load of 12 PS applied to the driven pulley.
- The driven belt was observed to determine whether cracks formed in the ribs. The time before the cords in the belt popped out was also measured. The data generated is reproduced in Table 7, below.
TABLE 7 Inventive Examples Comparative Samples 1 2 3 4 5 1 2 3 4 Peeling Force at room 530 550 550 530 500 300 200 Solidified 250 temperature (N/25 mm) Peeling Force at 100° C. (N/25 240 230 200 230 180 100 70 Solidified 90 mm) Peeling Force after thermal 329 360 280 350 280 150 140 Solidified 150 curing (120° C. × 8 days) (N/25 mm) Life of Belt (hrs), and Cause of — 1000 — — — 72 24 — 72 Failure *2 popped popped popped out out out - In the inventive examples, with the ratio by weight of the isocyanate compound to the nitrile rubber composition in the third processing liquid between 1/1 and 1/3, and with the solid content of the third processing liquid between 3-7%, the peeling force between the rubber and the fiber cords was high, as shown in FIGS. 4 and 5. Where the ratio by weight of the isocyanate compound to the acrylonitrile-butadiene rubber composition in the third processing liquid was larger than 2/1, the adhesive was solidified during treatment of the fibers due to its poor stability. Where the ratio was smaller than 1/3, the peeling force between the rubber and the fiber cords was greatly lowered.
- It was further observed that when the solid content of the third processing liquid was smaller than 3% or larger than 7%, the peeling force between the rubber and the fiber cords was lowered.
- The running tests verify that when the ratio by weight of the isocyanate compound to the acrylonitrile-butadiene rubber composition in the third processing liquid used falls between 1/1 and 1/3, and when the solid content of the third processing liquid falls between 3 and 7%, the peeling force between the fiber cords and the adhesive rubber layer in the belts is high. At the same time, the adhesive-processed cords remain flexible, with the result being that the life of the belts is long.
- The present invention makes possible the manufacture of an adhesive-processed fiber having good adhesion without requiring use of a halogen containing polymer. With the fiber used in load carrying cords in a power transmission belt, long belt life may result, even with the belt operating in a high temperature environment.
- The foregoing disclosure of specific embodiments is intended to be illustrative of the broad concepts comprehended by the invention.
Claims (32)
1. Processed fiber for bonding to a rubber composition, said processed fiber comprising:
unprocessed fiber treated with
a) a first processing liquid comprising at least one of an isocyanate compound and an epoxy compound,
b) a second processing liquid comprising RFL comprising at least one rubber latex selected from acrylonitrile-butadiene rubber latex and hydrogenated nitrile rubber latex, and
c) a third processing liquid comprising rubber paste comprising acrylonitrile-butadiene rubber composition dissolved in a solvent and an isocyanate compounds with the weight ratio of the isocyanate compound to the acrylonitrile-butadiene rubber composition being from 1/1 to 1/3, the third processing liquid having a solid content of from 3-7%.
2. The processed fiber according to wherein the fiber is treated with the second processing liquid after being treated with the first processing liquid and with the third processing liquid after being treated with the second processing liquid.
claim 1
3. The processed fiber according to wherein the fiber comprises at least one of polyethylene terephthalate fiber (PET), polyethylene naphthalate fiber (PEN), aramid fiber, and 6-nylon.
claim 1
4. The processed fiber according to wherein the fiber is treated with the first processing liquid for 0.5-30 seconds and thereafter heated at a temperature of 150-190° C. for from 2-5 minutes.
claim 1
5. The processed fiber according to wherein the RFL processing liquid is a mixture of resorcinol and formalin with rubber latex in which the molar ratio of resorcinol to formalin is from 3/1 to 1/3.
claim 1
6. The processed fiber according to wherein the RFL processing liquid is prepared by mixing a precondensate of resorcinol and formalin with rubber latex so that resin content is from 5 to 100 parts by weight relative to 100 parts by weight of rubber content in the rubber latex and so that the solid content of the RFL processing liquid is from 5 to 40%.
claim 5
7. The processed fiber according to wherein the fiber is treated with the second processing liquid at 5-40° C. for 0.5-30 seconds and thereafter heated at a temperature of 220-250° C. for from 1-3 minutes.
claim 6
8. The processed fiber according to wherein the fiber is treated with the third processing liquid at 5-40° C. for 0.5-30 seconds and thereafter heated at a temperature of from 140-180° C. for from 3-7 minutes.
claim 1
9. The processed fiber according to wherein the isocyanate compound in the first processing liquid comprises at least one of 4,4′-diphenylmethane diisocyanate, toluene 2,4-diisocyanate, polymethylene polyphenyldiisocynanate, hexamethylene diisocyanate, polyaryl polyisocyanate, and blocked polyisocyanate prepared by reacting an isocyanate compound with a blocking agent.
claim 1
10. The processed fiber according to wherein the acrylonitrile-butadiene rubber composition in the third processing liquid comprises acrylonitrile-butadiene rubber with at least one of a reinforcing agent, a filler, a softener, an anti-aging agent, and a vulcanization agent added thereto.
claim 1
11. The processed fiber according to wherein the epoxy compound in the first processing liquid comprises at least one of a reaction product of at least one of a polyalcohol and polyakylene glycol, a halogen-containing epoxy compound, and a reaction product of polyphenol.
claim 1
12. The processed fiber according to wherein the epoxy compound in the first processing liquid is mixed with an organic solvent.
claim 1
13. A power transmission belt comprising:
an endless body having a length; and
fiber embedded in the endless body,
wherein the fiber comprises:
a) a first processing liquid comprising at least one of an isocyanate compound and an epoxy compound,
b) a second processing liquid comprising RFL comprising at least one rubber latex selected from acrylonitrile-butadiene rubber latex and hydrogenated nitrile rubber latex, and
c) a third processing liquid comprising rubber paste comprising acrylonitrile-butadiene rubber composition dissolved in a solvent and an isocyanate compound, with the weight ratio of the isocyanate compound to the acrylonitrile-butadiene rubber composition being from 1/1 to 1/3, the third processing liquid having a solid content of from 3-7%.
14. The power transmission belt according to wherein the fiber defines a cord which extends lengthwise in the body.
claim 13
15. The power transmission belt according to wherein the body comprises a cushion layer made from rubber and the cord is embedded in the cushion layer and extends endlessly within the body.
claim 14
16. The power transmission belt according to wherein the compressible rubber comprises alkylated chlorosulfonated polyethylene with a low density polyethylene that has a linear molecular structure and is chlorosulfonated to have a chlorine content of from 15-35% by weight and a sulfur content of from 0.5-2.5% by weight.
claim 15
17. The power transmission belt according to wherein the power transmission belt is one of a V-belt and a V-ribbed belt.
claim 15
18. The power transmission belt according to wherein the power transmission belt is a toothed belt having teeth spaced from each other lengthwise of the body, the body has an inside layer in which the teeth are formed and a back layer and the cord is embedded in the back layer.
claim 15
19. The power transmission belt according to wherein the fiber is treated with the second processing liquid after being treated with the first processing liquid and with the third processing liquid after being treated with the second processing liquid.
claim 14
20. The power transmission belt according to wherein the fiber comprises at least one of polyethylene terephthalate fiber (PET), polyethylene naphthalate fiber (PEN), aramid fiber, and 6-nylon.
claim 14
21. The power transmission belt according to wherein the fiber is treated with the first processing liquid for 0.5-30 seconds and thereafter heated at a temperature of 150-190° C. for from 2-5 minutes.
claim 19
22. The power transmission belt according to wherein the RFL processing liquid is a mixture of resorcinol and formalin with rubber latex in which the molar ratio of resorcinol to formalin is from 3/1 to 1/3.
claim 14
23. The power transmission belt according to wherein the RFL processing liquid is prepared by mixing a precondensate of resorcinol and formalin with rubber latex so that resin content is from 5 to 100 parts by weight relative to 100 parts by weight of rubber content in the rubber latex and so that the solid content of the RFL processing liquid is from 5 to 40%.
claim 14
24. The power transmission belt according to wherein the fiber is treated with the second processing liquid at 5-40° C. for 0.5-30 seconds and thereafter heated at a temperature of 220-250° C. from 1-3 minutes.
claim 14
25. The power transmission belt according to wherein the fiber is treated with the third processing liquid at 5-40° C. for 0.5-30 seconds and thereafter heated at a temperature of from 140-180° C. for from 3-7 minutes.
claim 14
26. The power transmission belt according to wherein the isocyanate compound in the first processing liquid comprises at least one of 4,4′-diphenylmethane diisocyanate, toluene 2,4-diisocyanate, polymethylene polyphenyl-diisocynanate, hexamethylene diisocyanate, polyaryl polyisocyanate, and blocked polyisocyanate prepared by reacting an isocyanate compound with a blocking agent.
claim 14
27. The power transmission belt according to wherein the acrylonitrile-butadiene rubber composition in the third processing liquid comprises acrylonitrile-butadiene rubber with at least one of a reinforcing agent, a filler, a softener, an anti-aging agent, a vulcanization agent added thereto.
claim 14
28. The power transmission belt according to wherein the epoxy compound in the first processing liquid comprises at least one of a reaction product of at least one of a polyalcohol and polyakylene glycol, a halogen-containing epoxy compound, and a reaction product of polyphenol.
claim 14
29. The power transmission belt according to wherein the epoxy compound in the first processing liquid is mixed with an organic solvent.
claim 14
30. The power transmission belt according to wherein the body has a compression section comprising rubber comprising at least one of alkylated chlorosulfonated polyethylene (ACSM), hydrogenated nitrile rubber (H-NBR), nitrile-butadiene rubber (NBR), chloroprene rubber (CR), and chlorsulfonated polyethylene rubber (CSM).
claim 14
31. The power transmission belt according to wherein the body has a cushion rubber layer in which the cord is embedded and the cushion rubber layer comprises a hydrogenated nitrile rubber composition.
claim 15
32. The power transmission belt according to wherein the hydrogenated rubber composition comprises hydrogenated nitrile rubber to which is added at least one of a reinforcing agent, a filler, a softener, an anti-aging agent, a vulcanization promoter and a vulcanizing agent.
claim 31
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20532897 | 1997-07-14 | ||
JP205328/1997 | 1997-07-14 | ||
JP9-205328 | 1997-07-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
US20010055667A1 true US20010055667A1 (en) | 2001-12-27 |
US6358609B2 US6358609B2 (en) | 2002-03-19 |
Family
ID=16505116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/114,848 Expired - Lifetime US6358609B2 (en) | 1997-07-14 | 1998-07-14 | Processed fiber which is bondable to a rubber composition and a power transmission belt incorporating the processed fiber |
Country Status (4)
Country | Link |
---|---|
US (1) | US6358609B2 (en) |
EP (1) | EP0892007B1 (en) |
CA (1) | CA2243026C (en) |
DE (1) | DE69821058T2 (en) |
Cited By (3)
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US20090048048A1 (en) * | 2004-11-24 | 2009-02-19 | Bando Chemical Industries, Ltd. | V-ribbed belt and automotive accessory drive belt drive system using the same |
EP3323936A4 (en) * | 2015-07-15 | 2019-03-20 | Nippon Sheet Glass Company, Limited | Rubber reinforcement cord and rubber product using same |
US11905649B2 (en) | 2013-12-18 | 2024-02-20 | Teijin Frontier Co., Ltd. | Fiber cord for reinforcement and method for producing the same |
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EP1129125B1 (en) | 1999-08-23 | 2003-12-10 | Teijin Limited | Process for producing an adhesive-treated polyester fiber cord |
DE10101131A1 (en) * | 2000-02-09 | 2001-08-16 | Heidelberger Druckmasch Ag | Belt drive for printing machine comprises belt guide with guide surfaces for projections along edges of belt |
US6709758B2 (en) * | 2001-11-09 | 2004-03-23 | Lord Corporation | Room temperature curable X-HNBR coating |
US20030105218A1 (en) * | 2001-11-21 | 2003-06-05 | Lord Corporation | Room temperature curable oil resistant elastomer coating |
US7045201B2 (en) | 2002-06-14 | 2006-05-16 | The Goodyear Tire & Rubber Company | Starch-modified aqueous adhesive dip, treated yarns therewith and tire having component of rubber composition containing such treated yarns |
US7037578B2 (en) * | 2002-12-11 | 2006-05-02 | The Goodyear Tire & Rubber Company | Power transmission belt |
US7082998B2 (en) | 2003-07-30 | 2006-08-01 | Halliburton Energy Services, Inc. | Systems and methods for placing a braided, tubular sleeve in a well bore |
DE102004025225A1 (en) * | 2004-05-22 | 2005-12-08 | Contitech Antriebssysteme Gmbh | High-hybrid V-belts |
US7971856B2 (en) * | 2006-11-29 | 2011-07-05 | J.R. Clancy, Inc. | Drive rope and drive pulley |
KR101164728B1 (en) * | 2007-07-03 | 2012-07-12 | 더 게이츠 코포레이션 | Power transmission belt and variable speed belt drive comprising the belt |
US9944763B2 (en) | 2009-12-01 | 2018-04-17 | Gates Corporation | Polyurea-urethane cord treatment for power transmission belt and belt |
US20120067476A1 (en) * | 2010-09-20 | 2012-03-22 | Serge Julien Auguste Imhoff | Pneumatic tire and method for making a pneumatic tire |
DE102011054976A1 (en) | 2011-11-02 | 2013-05-02 | Contitech Antriebssysteme Gmbh | Process for the preparation of a tension member, in particular a carbon tension member, in the manufacture of a belt |
ITTO20120080A1 (en) * | 2012-01-31 | 2013-08-01 | Dayco Europe Srl | USE OF A TRANSMISSION BELT IN OIL AND ITS RELATIVE TRANSMISSION SYSTEM |
DE102012103867A1 (en) * | 2012-05-03 | 2013-11-07 | Contitech Antriebssysteme Gmbh | Drive belt with improved textile adhesion |
NL1039856C2 (en) * | 2012-10-22 | 2014-04-23 | Stichting Dutch Polymer Inst | Coated reinforcement fiber, process for the manufacturing of such fiber and polymer composite comprising such fiber. |
DE102013104757A1 (en) * | 2013-05-08 | 2014-11-13 | Contitech Antriebssysteme Gmbh | Method for producing a belt with prepared tension members with a cover layer |
US10220545B2 (en) * | 2016-04-30 | 2019-03-05 | Contitech Antriebssysteme Gmbh | Water based urethane as predip for carbon fiber cord |
JP6740494B1 (en) * | 2019-03-19 | 2020-08-12 | 三ツ星ベルト株式会社 | Processing agent for core wire for power transmission belt, core wire and manufacturing method thereof |
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GB774722A (en) * | 1953-11-24 | 1957-05-15 | Gen Tire & Rubber Co | Improvements in or relating to the adhesion of rubber bodies to fibres |
US4031288A (en) | 1971-11-11 | 1977-06-21 | The Goodyear Tire & Rubber Company | Bonding tire cord to rubber |
SU456811A1 (en) | 1972-06-06 | 1975-01-15 | Предприятие П/Я В-8749 | Impregnating compound for fixing textiles to rubber |
JPS54132647A (en) | 1978-04-06 | 1979-10-15 | Nippon Zeon Co Ltd | Vulcanizable rubber composition having improved ozon crack and oil resistance |
JPS55135244A (en) * | 1979-04-05 | 1980-10-21 | Mitsuboshi Belting Ltd | Power transmission belt |
US4501791A (en) * | 1982-03-09 | 1985-02-26 | Burlington Industries, Inc. | Non-woven fabric for V-belt bead wrap and chafer |
US4762745A (en) | 1983-02-28 | 1988-08-09 | Mitsuboshi Belting Ltd. | Rubber/fabric composite manufacture |
JPH0641527B2 (en) | 1988-07-06 | 1994-06-01 | バンドー化学株式会社 | Method of bonding hydrogenated nitrile rubber compound to fiber |
JPH0641525B2 (en) | 1988-07-06 | 1994-06-01 | バンドー化学株式会社 | Method of bonding hydrogenated nitrile rubber compound to fiber |
US4978409A (en) | 1988-07-06 | 1990-12-18 | Bando Chemical Industries, Ltd. | Method of bonding fibers to hydrogenated nitrile rubber |
US5219902A (en) | 1990-01-25 | 1993-06-15 | Mitsuboshi Belting Ltd | Method of bonding a hydrogenated nitrile rubber composition with fibers and articles |
JPH0641528B2 (en) * | 1990-01-25 | 1994-06-01 | 三ツ星ベルト株式会社 | Method for bonding hydrogenated nitrile rubber composition to fiber |
JP3113027B2 (en) * | 1991-12-17 | 2000-11-27 | 株式会社椿本チエイン | Toothed belt and method of manufacturing the same |
JP2983894B2 (en) * | 1995-11-27 | 1999-11-29 | バンドー化学株式会社 | Transmission belt |
-
1998
- 1998-07-13 CA CA002243026A patent/CA2243026C/en not_active Expired - Fee Related
- 1998-07-14 EP EP98250257A patent/EP0892007B1/en not_active Expired - Lifetime
- 1998-07-14 US US09/114,848 patent/US6358609B2/en not_active Expired - Lifetime
- 1998-07-14 DE DE69821058T patent/DE69821058T2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090048048A1 (en) * | 2004-11-24 | 2009-02-19 | Bando Chemical Industries, Ltd. | V-ribbed belt and automotive accessory drive belt drive system using the same |
US11905649B2 (en) | 2013-12-18 | 2024-02-20 | Teijin Frontier Co., Ltd. | Fiber cord for reinforcement and method for producing the same |
EP3323936A4 (en) * | 2015-07-15 | 2019-03-20 | Nippon Sheet Glass Company, Limited | Rubber reinforcement cord and rubber product using same |
US10913830B2 (en) | 2015-07-15 | 2021-02-09 | Nippon Sheet Glass Company, Limited | Rubber-reinforcing cord and rubber product including same |
Also Published As
Publication number | Publication date |
---|---|
EP0892007A3 (en) | 1999-07-21 |
DE69821058D1 (en) | 2004-02-19 |
US6358609B2 (en) | 2002-03-19 |
EP0892007A2 (en) | 1999-01-20 |
EP0892007B1 (en) | 2004-01-14 |
CA2243026C (en) | 2007-01-16 |
CA2243026A1 (en) | 1999-01-14 |
DE69821058T2 (en) | 2004-12-09 |
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