WO2007129624A1 - 補強用コードおよびその製造方法、並びに、その補強用コードを用いた製品 - Google Patents
補強用コードおよびその製造方法、並びに、その補強用コードを用いた製品 Download PDFInfo
- Publication number
- WO2007129624A1 WO2007129624A1 PCT/JP2007/059237 JP2007059237W WO2007129624A1 WO 2007129624 A1 WO2007129624 A1 WO 2007129624A1 JP 2007059237 W JP2007059237 W JP 2007059237W WO 2007129624 A1 WO2007129624 A1 WO 2007129624A1
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- WIPO (PCT)
- Prior art keywords
- reinforcing
- coating layer
- reinforcing cord
- latex
- forming
- Prior art date
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Classifications
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
- D02G3/404—Yarns or threads coated with polymeric solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/06—Rod-shaped
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
- B29C48/154—Coating solid articles, i.e. non-hollow articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0042—Reinforcements made of synthetic materials
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/12—General methods of coating; Devices therefor
- C03C25/18—Extrusion
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/27—Rubber latex
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/30—Polyolefins
- C03C25/305—Polyfluoroolefins
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/323—Polyesters, e.g. alkyd resins
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/48—Coating with two or more coatings having different compositions
- C03C25/50—Coatings containing organic materials only
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D11/00—Other features of manufacture
- D01D11/06—Coating with spinning solutions or melts
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/447—Yarns or threads for specific use in general industrial applications, e.g. as filters or reinforcement
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- 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
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
- B29C48/34—Cross-head annular extrusion nozzles, i.e. for simultaneously receiving moulding material and the preform to be coated
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/10—Cords, strands or rovings, e.g. oriented cords, strands or rovings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2221/00—Use of unspecified rubbers as reinforcement
- B29K2221/003—Thermoplastic elastomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2029/00—Belts or bands
Definitions
- the present invention relates to a reinforcing cord and a manufacturing method thereof, and a product reinforced with the reinforcing cord, and more particularly, reinforced with a reinforcing cord for rubber, a manufacturing method thereof, and the reinforcing cord. Related to rubber products.
- JP-A-11-217739 several glass fibers impregnated with latex are bundled, dried, twisted, and if necessary, an aqueous solution containing latex on the glass fiber.
- a technique for improving both bending resistance and water / oil resistance by applying a fiber treatment agent to form a coating layer is disclosed.
- the coating layer formed by the method of immersing the fiber in the treatment agent or applying the treatment agent to the fiber is likely to contain fine pores resulting from the production method. It was difficult to completely prevent the intrusion of oil and oil. Therefore, it is difficult to further improve the durability of products such as toothed belts using the reinforcing cord formed by the above method. Met.
- JP-A-11-13836, JP-A-2004-17378, and JP-A-2004-316049 address such a problem by extruding a rubber material with an extruder to the surface of a reinforcing fiber.
- a technique for forming a rubber layer covering a reinforcing fiber by being deposited thereon is disclosed. Since the rubber layer formed in this way is unlikely to have fine holes, it prevents water or oil from entering the inside of the reinforcing cord of the rubber layer and reducing its strength. be able to.
- the rubber layer (covering layer) is formed on the surface of the reinforcing fiber by extruding the material, it has sufficient heat resistance and creep resistance (shape stability). Since the coating layer could not be obtained, there was a problem that the coating layer was damaged during the long-term actual use and water or oil entered the cord. In addition, when the coating layer (rubber layer) is formed by such a method, it is difficult to form a uniform and thin layer, and the outer shape of the reinforcing cord becomes large.
- the present invention has been made paying attention to the problems as described above, and can achieve good water resistance and oil resistance by suppressing the penetration of water and oil into the reinforcing cord, and To provide a reinforcing cord capable of realizing good bending resistance by preventing the fiber from being untwisted by bending and a manufacturing method thereof, and to provide a product using the reinforcing cord as a reinforcing material. Objective.
- the method for manufacturing a reinforcing cord according to the present invention is a method for manufacturing a reinforcing cord including a reinforcing fiber bundle including a plurality of reinforcing fibers and a coating layer provided on a surface of the reinforcing fiber bundle.
- a polyester-based thermoplastic elastomer and a fluoro-resin-based thermoplastic elastomer The method includes the step of forming the coating layer by extruding a material containing at least one selected from a streamer and adhering the extruded material to the surface of the reinforcing fiber bundle.
- extrusion molding a method of extruding a material and adhering it to the surface of a reinforcing fiber bundle when forming a coating layer.
- the reinforcing cord of the present invention is manufactured using the manufacturing method of the present invention described above.
- the product of the present invention includes the above-described reinforcing cord of the present invention as a reinforcing material.
- the reinforcing cord obtained by the reinforcing cord of the present invention and the reinforcing cord obtained by the production method of the present invention is a polyester-based thermoplastic elastomer obtained by extrusion molding.
- a coating layer containing at least one selected from mono- and fluoro-resin-based thermoplastic elastomers is formed.
- the reinforcing cord obtained by the present invention since a thermoplastic elastomer is used when forming the coating layer by extrusion molding, it is thinner and has a uniform thickness compared to the case of using rubber. A film can be produced. Therefore, according to the present invention, it is possible to obtain an effect that the outer shape of the reinforcing cord can be finely finished. In the current technology, it is difficult to extrude a thin and uniform film using a rubber material. In general, when rubber material is used, the minimum thickness that can be practically formed is about 0.3 mm. On the other hand, when a thermoplastic elastomer is used, the thickness can be reduced to about 0.1 mm.
- the reinforcing fiber bundle inside thereof is firmly bound by the covering layer formed by extrusion molding even after long-term use. For this reason, it is possible to realize good bending resistance that makes it difficult to untwist the reinforcing fiber bundle even under severe conditions of bending. Therefore, the bending resistance of the product of the present invention using this reinforcing cord can be dramatically improved.
- the reinforcing cord obtained by the present invention has sufficient oil resistance and water resistance, it is necessary to form a base coating layer using a material excellent in oil resistance and water resistance. There is no need. Therefore, even when a base coating layer is formed below the coating layer, a low cost and material (for example, aqueous solution of latex resin) can be selected, so that the manufacturing cost of the reinforcing cord can be reduced. Is also possible.
- the reinforcing cord obtained by the present invention is excellent in durability such as flex resistance, water resistance, and oil resistance. Therefore, the product of the present invention including this reinforcing cord as a reinforcing material is also excellent in durability.
- FIG. 1 is a schematic diagram showing a schematic configuration of an example of an extruder used for forming a coating layer of a reinforcing cord of the present invention.
- FIG. 2 is a schematic cross-sectional view illustrating an example of a crosshead portion of the extruder shown in FIG.
- FIG. 3 is a drawing-substituting photograph in which the surface of the coating layer was observed with a scanning electron microscope for the example of the reinforcing cord of the present invention.
- FIG. 4A is a schematic cross-sectional view showing a configuration of an example of a reinforcing cord of the present invention.
- FIG. 4B is a schematic cross-sectional view showing the configuration of a flat belt as an example of a product reinforced with the reinforcing cord of the present invention.
- FIG. 5 is a schematic diagram for explaining a bending test apparatus.
- the reinforcing cord manufacturing method of the present embodiment includes at least one kind of polyester thermoplastic elastomer and fluororesin thermoplastic elastomer marker selected by extrusion molding on the surface of the reinforcing fiber bundle. Including a step of forming a covering layer.
- the reinforcing cord manufacturing method of the present embodiment may further include a step of twisting the reinforcing fibers to form a reinforcing fiber bundle prior to the step of forming the covering layer.
- the method for manufacturing a reinforcing cord of the present embodiment may include a step of forming a base coating layer on the surface of the reinforcing fiber before the step of forming the coating layer.
- the reinforcing fiber formed with the base coating layer is twisted to form a reinforcing fiber bundle.
- Process May further be included.
- the base coating layer can be formed using a fiber treatment agent containing rubber latex. As rubber latex, for example
- the method for manufacturing a reinforcing cord of the present embodiment further includes a step of forming an overcoat layer on the coating layer using a material including rubber, after the step of forming the coating layer.
- a material including rubber for example, a rubber containing chlorosulfonated polyethylene as a main component can be used.
- Rubber containing chlorosulfone polyethylene as the main component means that the content of chlorosulfone polyethylene in the entire rubber component is 50% by mass or more.
- the reinforcing fiber used in the method for manufacturing the reinforcing cord of the present embodiment is not particularly limited in material and shape as long as it has a function of reinforcing the product.
- the reinforcing fibers include glass fibers, polyvinyl alcohol fibers typified by vinylon fibers, polyester fibers, nylon, aramid (aromatic polyamide), and other polyamide fibers, polyarylate fibers, polyketone fibers, and carbon fibers.
- polyparaphenylene benzoxazole (PBO) fibers can be used.
- glass fibers excellent in dimensional stability, heat resistance, tensile strength, etc. are preferably used.
- the type of glass in the glass fiber is not particularly limited, but high strength glass excellent in tensile strength is preferable to general alkali-free glass.
- the configuration of the fiber is not particularly limited.
- the average diameter of the filament, which is the minimum constituent unit of the fiber is 5 to 13 ⁇ m.
- 50 to 2000 filaments are bundled with a sizing agent, and one or more filaments are bundled to produce a reinforcing fiber.
- a reinforcing fiber bundle is prepared by arranging a plurality of reinforcing fibers.
- a coating layer is formed on the surface of the reinforcing fiber bundle by extrusion. A method for forming the coating layer will be described later.
- the method of forming the reinforcing fiber bundle is not limited to the above method, and no upper twisting is performed! / The one in which the directions of the lower twist and the upper twist are the same, or the reinforcing fiber Various configurations can be used, such as those in which fibers of different materials are used in the central portion and the outer layer portion of the bundle, or those in which the direction of the upper twist is changed if the lower twist is used.
- the reinforcing fiber bundle in the present embodiment is formed by converging a plurality of reinforcing fibers.
- the reinforcing fiber bundle is formed with a reinforcing fiber whose surface is previously coated with a base coating layer.
- a reinforcing fiber bundle may be formed using this reinforcing fiber. Details of the base coating layer will be described later.
- the reinforcing cord in the present embodiment includes a coating layer formed by extrusion molding.
- This coating layer is preferably flexible (highly elastic) in order to improve bending resistance. Therefore, a material having flexible elastomer properties at room temperature is preferably used.
- the term “flexible elastomericity” as used herein means, for example, having a hardness of 100 or less in Shore hardness (JIS K 6253) or 80 or less in Shore D hardness (JIS K 6253).
- the coating layer in the present embodiment is made of a polyester-based thermoplastic elastomer and a fluorine soot because it is difficult for deformation and damage to occur even during long-term use and has excellent moldability and film thickness controllability.
- At least selected from a fatty thermoplastic elastomer It is formed using a material including one kind.
- the material for forming the coating layer preferably contains 20% by mass or more of at least one selected from a polyester-based thermoplastic elastomer and a fluoro-resin-based thermoplastic elastomer, more preferably 50% by mass.
- polyester-based thermoplastic elastomer 100% by mass, that is, it is formed of at least one selected from polyester-based thermoplastic elastomer and fluorine-resin-based thermoplastic elastomer.
- polyester-based thermoplastic elastomers and fluorocoagulant-based thermoplastic elastomers they are exposed in the process of forming an overcoat layer after forming the covering layer and the process of embedding a reinforcing cord in the matrix. It is desirable to select materials that do not melt or foam in the temperature range.
- the coating layer is also required to have adhesive strength with the matrix and overcoat layer, it is more desirable to use a V ⁇ material for the coating layer, which is similar to the material used for the matrix and overcoat layer.
- the coating layer is preferably formed of a material containing a polyester-based thermoplastic elastomer because of its superior adhesion and other properties to the materials generally used for the matrix and overcoat layer. It is desirable to use a material containing 50% by mass or more of a polyester-based thermoplastic elastomer.
- polyester-based thermoplastic elastomer examples include “No Itoler” manufactured by Toray DuPont Co., Ltd., “Perprene” manufactured by Toyobo Co., Ltd., Dainippon Ink & Chemicals, Inc. "Glaisle” manufactured by Teijin Limited and “Nuyuberan” manufactured by Teijin Limited.
- fluoroelastomer thermoplastic elastomers examples include “DAIEL THERMO BLASTIC” manufactured by Daikin Industries, Ltd., “THV” manufactured by Sumitomo 3EM Co., Ltd., and the like.
- the material for forming the coating layer includes short glass fibers, carbon black, silica, or various organic fibers for the purpose of variously changing the moldability, molding conditions, or properties after molding. May be included.
- the coating layer formed of the material including at least one selected from the polyester-based thermoplastic elastomer and the fluorine-coagulated thermoplastic elastomer and formed by extrusion molding is impregnated with latex.
- the material is denser (fine holes are less likely to exist.) O
- the covering layer in the embodiment is strong in material and formed integrally by extrusion, so that it has a strong force to bind the objects inside. For this reason, it is excellent in maintaining the structure of the internal reinforcing fiber bundle. This function is remarkable in the reinforcing cord in which the reinforcing fiber is twisted.
- a material containing at least one selected from a polyester-based thermoplastic elastomer and a fluorine-resin-based thermoplastic elastomer can be selected.
- a coating layer with excellent properties (shape stability) is formed, and a reinforcing cord that can withstand long-term use can be produced.
- the thickness of the coating layer is not particularly limited, but can be set, for example, in the range of 0.05 to 5. Omm.
- the reasoning force to reduce the overall cord diameter is 0.05 to 5. 1. It is preferable to be in the range of Omm.
- the material of the coating layer is continuously formed on the surface of the reinforcing fiber bundle moving relative to the extruder by extruding the material of the coating layer described above with an extruder.
- a coating layer is formed by using an extruder as shown in FIGS.
- FIG. 1 shows a schematic configuration of an example of an extruder used for forming a coating layer.
- the extruder 1 includes an extrusion mechanism unit 11 and a crosshead unit 15.
- the extruding mechanism unit 11 includes a cylinder 12, a screw 13, and a heater (not shown).
- the material 14 for forming the coating layer is supplied from a hopper (not shown) into the cylinder 12, heated and melted by a heater, and sent to the crosshead portion 15 by the rotation of the screw 13.
- the fed material 14 is pushed out onto the surface of the reinforcing fiber bundle 21 that moves in one direction with respect to the crosshead portion 15 of the extruder 1 by a transport mechanism (not shown).
- a coating layer is formed. In this way, the reinforcing cord 2 is manufactured.
- FIG. 2 shows an enlarged cross-sectional view of an example of the crosshead portion 15.
- the crosshead portion 15 is constituted by dies 16, 17 and a cored bar 18 having a land portion.
- the molten material 14 is fed by the extrusion mechanism. come.
- the material 14 is extruded onto the surface of the reinforcing fiber bundle 21 to form a covering layer 22 and complete the reinforcing cord 2.
- the dice are divided, but the present invention is not limited to this.
- the structure of the extruder shown in FIGS. 1 and 2 is an example, and is not limited to this.
- the apparatus includes a mechanism that can extrude the material and adhere it onto the surface of the reinforcing fiber bundle. Any structure can be used.
- the reinforcing cord of the present embodiment it is desirable to provide a base coating layer in advance on the reinforcing fiber in order to achieve better bending resistance and strength.
- the base coating layer can be formed, for example, by immersing reinforcing fibers such as the above-described glass fibers in a fiber treatment agent containing rubber latex and then drying the fibers.
- the product to be reinforced is required to have particularly high strength and bending resistance, it is preferable to provide a base coating layer on the reinforcing fiber. This is because by providing the base coating layer, the reinforcing fibers do not directly touch each other, so that the reinforcing fibers can be prevented from being damaged and the strength of the reinforcing cords can be improved in bending resistance. .
- This base coating layer can be formed by applying an aqueous fiber treatment agent containing rubber latex to the reinforcing fibers (hereinafter sometimes referred to as an aqueous treatment agent) and drying and curing it.
- an aqueous treatment agent containing rubber latex
- drying and curing it the base coating layer will be described in detail.
- the base coating layer of the present embodiment can be formed using an aqueous treatment agent containing rubber latex as a main component.
- This rubber latex includes, for example, bullpyridine 'styrene' butadiene terpolymer latex, butadiene latex, butadiene 'styrene copolymer latex, dicarboxylated butadiene' styrene copolymer latex, ethylene propylene latex, chlorosulfonated.
- At least one selected from polyethylene latex, fluororubber latex, acrylic rubber latex and hydrogenated-tolyl rubber latex force can be used.
- the rubber latex contained in the aqueous treatment agent may be one or more of the examples shown above. “Containing rubber latex as the main agent” means that the content of rubber latex with respect to the fiber treatment agent is 20% by mass or more.
- the aqueous treatment agent may contain polyurethane resin, epoxy resin, acrylic resin, phenol resin, melamine resin, emulsion of low molecular polyolefin resin, or water-dispersed resin.
- the aqueous treatment agent may contain a resorcin formaldehyde condensate for the purpose of improving the adhesion between the reinforcing fiber and the latex.
- the aqueous treatment agent may contain carbon black.
- carbon black as an inexpensive inorganic filler, the manufacturing cost of the reinforcing cord can be reduced.
- the aqueous treatment agent may appropriately contain other constituents such as an inorganic filler other than carbon black, a plasticizer, an anti-aging agent, a metal oxide, a crosslinking agent, or a crosslinking aid.
- an inorganic filler include silica particles.
- Aqueous processing agent strength Resorcinol Both formaldehyde condensate and carbon black may be included.
- the aqueous treatment agent preferably has a form in which the constituent components of the base coating layer are dispersed in an aqueous solvent.
- the content ratio of the constituent components of the base coating layer in the aqueous treatment agent is a solid mass ratio when the mass of the rubber latex is 100, and the resorcin formaldehyde condensate is preferably in the range of 0 to 100! / ,. If there is too much resorcin formaldehyde condensate contained in the aqueous fiber treatment agent, the rubber latex will be relatively less, so the hardness of the undercoat layer will be too high, resulting in a decrease in the bending resistance of the product. For this reason, the content ratio of the resorcin-formaldehyde condensate is more preferably in the range of 5-30.
- the method for forming the base coating layer by applying an aqueous treatment agent to the reinforcing fiber is not particularly limited. Is not something Usually, the base coating layer can be formed by immersing the reinforcing fiber in a water tank containing an aqueous treatment agent, pulling it up, and removing the water in a drying furnace. Moreover, although the drying conditions for removing water are not limited, for example, it may be exposed in an atmosphere of 80 to 320 ° C. for 0.1 to 2 minutes.
- the adhesion rate of the base coating layer will be described.
- the adhesion rate R of the undercoat layer is a mass percentage indicating how much the undercoat layer adheres to the mass of the reinforcing fiber such as glass fiber in the reinforcing cord after drying. It is given by the formula.
- Dry mass of reinforcing fiber before coating co
- Dry mass of reinforcing fiber after coating C1
- the adhesion rate of the base coating layer is preferably 10 to 30% by mass, and more preferably 12 to 25% by mass. When the adhesion rate is less than 10% by mass, it is difficult to cover the entire surface of the reinforcing fiber bundle with the base coating layer.
- an overcoat layer may be provided on the covering layer for the purpose of further improving the adhesive strength with the matrix.
- the treatment agent for forming this overcoat layer can contain, for example, rubber, a cross-linking agent, carbon black, a solvent and an adhesive.
- rubber contained in this treating agent for example, rubber containing chlorosulfonated polyethylene as a main component is preferably used.
- the thickness of the overcoat layer is not particularly limited, but can be set, for example, within a range of 5 to: LOO / zm.
- the overcoat layer in the present embodiment can be formed using a generally known method.
- the overcoat layer can be formed by applying a treatment agent to the surface of the reinforcing cord on which the coating layer is formed and drying it.
- the coating and drying steps may be repeated a plurality of times.
- the overcoat layer is effective in improving the adhesion between the reinforcing cord and the matrix.
- a product reinforced with the reinforcing cord By embedding the reinforcing cord of the present embodiment obtained as described above in the matrix, a product reinforced with the reinforcing cord can be manufactured.
- a reinforcing cord in the rubber matrix By embedding a reinforcing cord in the rubber matrix, a rubber product reinforced with the reinforcing cord can be manufactured.
- the means for embedding and arranging the reinforcing cord of the present embodiment in the matrix of a product such as a belt is not particularly limited.
- the reinforcing cord when used as a reinforcing material for a toothed belt, the reinforcing cord can be embedded in the matrix by means generally used in the manufacture of a toothed belt for automobiles or printers.
- the product thus obtained has high durability since the reinforcing cord of the present embodiment is embedded.
- the product to be reinforced is a belt
- examples of the belt matrix include hydrogenated tolyl rubber and hydrogenated tolyl rubber in which zinc methacrylate is finely dispersed, chloroprene rubber, and ethylene propylene rubber.
- Polymers such as rubber as the main component or polyurethane can be preferably applied.
- polyester thermoplastic elastomer or fluororesin thermoplastic elastomer used for forming the coating layer is used as the belt matrix, an overcoat layer is provided on the reinforcing cord. Even if not, sufficient adhesion can be obtained between the reinforcing cord and the matrix.
- Example 1 three glass fibers (200 filaments of E glass composition with an average diameter of 9 ⁇ m bundled together) were drawn together and immersed in a water bath containing the aqueous treatment agent shown in Table 1 below. After pulling up, it was dried for 1 minute in a drying oven set at 150 ° C. to form a base coating layer, which was used as a reinforcing fiber.
- the glass fiber was twisted 8 times with ZlOcm, 11 of the twisted strands were gathered, and 8 times of ZlOcm was twisted to make a reinforcing fiber bundle.
- the adhesion rate of the base coating layer was 20% by mass with respect to the mass of the reinforcing fiber bundle.
- the extruder shown in Fig. 1 was used to produce a polyester-based thermoplastic elastomer, Toray DuPont's Hytorel (registered trademark) 727 7 was used to form a coating layer having a thickness of about 0.1 mm.
- the temperature when forming the coating layer is 220 ° C.
- Fig. 3 shows a result of observation of the surface of the reinforcing cord of this example, in which the coating layer was formed by extrusion molding, with a scanning electron microscope (SEM, JEOL Ltd., JSM-T330A). Showed the fruit. The shooting conditions were a pressurization voltage of 20 kV.
- SEM scanning electron microscope
- JSM-T330A scanning electron microscope
- the shooting conditions were a pressurization voltage of 20 kV.
- the surface of the coating layer formed by extrusion which is a feature of the present invention, is very smooth, and there are no fine holes that allow water or oil to enter. I got it.
- the thickness of the coating layer was about 0.1 mm, and the outer diameter of the cord was 1.4 mm compared to 1.2 mm before coating.
- an overcoat layer was formed on the reinforcing cord.
- An overcoat layer was formed by applying a mixture of chlorosulfone polyethylene, isocyanate, carbon black, P--trosobenzene, xylene and toluene and drying it. In this example, the overcoat layer was formed by repeating the coating and drying steps twice.
- FIG. 4A shows a schematic cross-sectional view of the reinforcing cord of this example manufactured as described above.
- the base coating layer 23 is formed on the surface of the glass fiber 20 in which a plurality of filaments are bundled, and the reinforcing fiber bundle 21 is formed by twisting the glass fiber 20.
- a covering layer 22 is formed on the surface of the reinforcing fiber bundle 21.
- an overcoat layer 24 is formed on the surface of the coating layer 22 to form the reinforcing cord 2 of this embodiment.
- hatching is used to make the outline easier to see. No application was made.
- the reinforcing cord of this example was embedded in the manner of press molding, and formed into a flat belt having a width of 19 mm and a thickness of 5 mm.
- the belt part length was 300 mm.
- FIG. 4B shows a schematic cross-sectional view of the flat belt 3 produced in this example.
- a reinforcing cord 2 is embedded in a rubber 31 that is a matrix.
- the product (flat belt) thus obtained was evaluated for durability. Specifically, the flat belt was subjected to a bending test apparatus 5 as shown in FIG. 5, the tensile strength of the flat belt before and after the test was determined, and the strength retention was determined from these strengths. The strength retention was calculated by the following formula, and the durability of the product was evaluated using this index. The tensile strength is measured by chucking a 250 mm long sample, pulling this sample in the length direction at a speed of 50 mm / min, and reading the maximum stress value until the cord (sample) breaks. did.
- the bending test apparatus 5 is first provided with a heating bath 50 that creates a test environment.
- One end of the reinforcing cord 2 is connected to the linear motor 51, and is sequentially hung on the pulleys 52 and 52.
- the flat belt 3 is bent by a roller 53, and the periphery of the roller 53 is stored in a heating bath 50.
- the other end of the reinforcing cord 2 is sequentially stretched over pulleys 52 and 52 and connected to a weight 54.
- the heating bath 50 has a structure in which a liquid 55 (in this case, water or oil) can be put into a bending test.
- the environmental conditions for the bending test were the following heat resistance test, water injection test, and oil injection test, and the number of bendings was 20000.
- Oil lubrication test Oil was added to heating bath 50 and set to 120 ° C
- Table 3 also shows the results of measuring the water absorption by immersing the reinforcing cord of this example in 96 ° C hot water for 24 hours. Furthermore, Table 3 also shows the results of measuring the oil absorption rate by immersing the reinforcing cord of this example in 120 ° C oil for 24 hours.
- the water absorption rate and oil absorption rate shown here are values obtained by measuring the weight of the reinforcing cord before and after dipping, and calculating the percentage divided by the weight before dipping before and after dipping. is there.
- the reinforcing cord of Example 2 was configured to omit the base coating layer (no base coating layer was provided) over the reinforcing cord of Example 1.
- other configurations were the same as those of the reinforcing cord of Example 1, and the same method was used.
- a flat belt was manufactured in the same manner as in Example 1.
- the reinforcing cord of Comparative Example 1 was configured such that the covering layer was omitted from the reinforcing cord of Example 1 (no covering layer was provided). However, the rest of the configuration was the same as that of Example 1, and the same method was used.
- the reinforcing cord of Comparative Example 2 is a force using TR1086 manufactured by JSR, which is a styrene thermoplastic elastomer as the material of the coating layer. It was made with.
- TR1086 manufactured by JSR
- JSR styrene thermoplastic elastomer
- Comparative Example 3 Resin P-206O manufactured by Dainichi Seika Kogyo Co., Ltd., which is a polyurethane elastomer, was used as the material for the coating layer. It was produced by the method.
- H-NBR Water-soluble hydrogenated diaryl rubber
- Example 1 in which the coating layer is made of a polyester-based thermoplastic elastomer is Compared with the reinforcing cords of Comparative Example 2 and Comparative Example 3 formed of a styrene-based thermoplastic elastomer and having a coating layer, the strength retention rate in the bending test is high. The result was obtained. As a result, the coating layer is formed using a polyester-based thermoplastic elastomer. It was confirmed that the bending resistance can be improved by forming.
- Example 2 Further, from the results of Example 2, by forming the coating layer with a polyester-based thermoplastic elastomer, a base coating layer is provided, and even in this case, sufficient water resistance and oil resistance can be obtained. It was also confirmed that there was no problem with the strength.
- the reinforcing cords of Examples 3 and 4 and Comparative Example 4 were prepared in the same manner except that the overcoat layer was omitted in Example 2 and Comparative Example 1, respectively.
- the coating layer was manufactured using THVX815G manufactured by Sumitomo 3M Co., which is a fluorocoagulant thermoplastic elastomer.
- THVX815G manufactured by Sumitomo 3M Co.
- the water absorption rate and oil absorption rate were measured in the same manner as in Example 1. The results are shown in Table 4.
- H-NBR Water-soluble hydrogen trill rubber
- Polyester elastomers and fluorocoagulant elastomers are all characterized by excellent balance of heat resistance, cold resistance, oil resistance and the like. Of these, polyester elastomers are excellent in mechanical properties and adhesive properties, and are suitable for use as rubber reinforcing cords. For comparison, the thickness of the force covering layer produced by using NBR (nitrile rubber) to form a reinforcing cord with a covering layer formed by extrusion cannot be reduced to 0.1 mm. The coating layer was 3mm thick and the force was not obtained. Also, this cord has an outer diameter of 1.8mm and 7 pieces.
- the use of a rubber material for the covering layer is not suitable for applications such as a timing belt in which the strength is reinforced by a plurality of reinforcing cords and the strength is maintained at a certain width. it is conceivable that.
- a reinforcing cord having good water resistance, oil resistance and bending resistance can be obtained. Therefore, according to the present invention, it can be suitably used to reinforce a product using a polymer material such as rubber or polyurethane as a matrix. Since the product reinforced with the reinforcing cord of the present invention can withstand a high load, it can be applied to various uses such as a toothed belt that require durability. In addition, the reinforcing cord of the present invention can be used as a substitute for an organic fiber rope or steel wire, and the bending resistance is improved compared to these cords and it can have a long life.
Abstract
Description
Claims
Priority Applications (4)
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JP2008514458A JP4843032B2 (ja) | 2006-05-01 | 2007-04-27 | 補強用コードおよびその製造方法、並びに、その補強用コードを用いた製品 |
CN2007800155782A CN101460673B (zh) | 2006-05-01 | 2007-04-27 | 加固用绳及其制造方法和使用该加固用绳的制品 |
BRPI0711130A BRPI0711130B1 (pt) | 2006-05-01 | 2007-04-27 | método para produzir um cordão de reforço, bem como cordão de reforço e produto contendo um cordão de reforço |
EP07742672.4A EP2014824B8 (en) | 2006-05-01 | 2007-04-27 | Reinforcing cord, method for producing the same, and product using the reinforcing cord |
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JP2006-127867 | 2006-05-01 | ||
JP2006127867 | 2006-05-01 |
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PCT/JP2007/059237 WO2007129624A1 (ja) | 2006-05-01 | 2007-04-27 | 補強用コードおよびその製造方法、並びに、その補強用コードを用いた製品 |
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EP (1) | EP2014824B8 (ja) |
JP (1) | JP4843032B2 (ja) |
CN (1) | CN101460673B (ja) |
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WO (1) | WO2007129624A1 (ja) |
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JP2016210027A (ja) * | 2015-04-30 | 2016-12-15 | 東レ・デュポン株式会社 | 繊維強化複合材及びその成形体 |
JP6132949B1 (ja) * | 2016-03-30 | 2017-05-24 | バンドー化学株式会社 | 歯付ベルトの製造方法 |
CN107866954A (zh) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | 连续纤维增强热塑性树脂预浸带的制造方法及设备 |
US20180229415A1 (en) * | 2015-07-30 | 2018-08-16 | Habasit Ag | System and method for manufacturing flightless, monolithic belt |
US10913830B2 (en) | 2015-07-15 | 2021-02-09 | Nippon Sheet Glass Company, Limited | Rubber-reinforcing cord and rubber product including same |
US11560671B2 (en) | 2017-06-19 | 2023-01-24 | Nippon Sheet Glass Company, Limited | Rubber-reinforcing cord and rubber product including same |
US11577455B2 (en) | 2012-08-29 | 2023-02-14 | Continuous Composites Inc. | Method and apparatus for continuous composite three-dimensional printing |
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CN102230247A (zh) * | 2011-06-20 | 2011-11-02 | 昆山维信纺织工业有限公司 | 一种纱线 |
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WO2015031226A1 (en) * | 2013-08-28 | 2015-03-05 | E. I. Du Pont De Nemours And Company | Fibrous cord and method of making |
CN111593513A (zh) * | 2020-05-21 | 2020-08-28 | 利辛县佳辉服饰有限公司 | 一种高强度的高分子针织纤维生产设备及方法 |
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Also Published As
Publication number | Publication date |
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CN101460673A (zh) | 2009-06-17 |
JPWO2007129624A1 (ja) | 2009-09-17 |
CN101460673B (zh) | 2011-06-22 |
EP2014824B8 (en) | 2014-03-12 |
EP2014824A1 (en) | 2009-01-14 |
BRPI0711130B1 (pt) | 2017-03-21 |
JP4843032B2 (ja) | 2011-12-21 |
EP2014824A4 (en) | 2013-07-24 |
EP2014824B1 (en) | 2014-01-29 |
BRPI0711130A2 (pt) | 2011-08-30 |
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