WO2017183660A1 - Rubber-reinforcing cord and rubber product using same - Google Patents

Rubber-reinforcing cord and rubber product using same Download PDF

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Publication number
WO2017183660A1
WO2017183660A1 PCT/JP2017/015756 JP2017015756W WO2017183660A1 WO 2017183660 A1 WO2017183660 A1 WO 2017183660A1 JP 2017015756 W JP2017015756 W JP 2017015756W WO 2017183660 A1 WO2017183660 A1 WO 2017183660A1
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Prior art keywords
rubber
reinforcing cord
coating
rubber reinforcing
filament bundle
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PCT/JP2017/015756
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French (fr)
Japanese (ja)
Inventor
将盛 古澤
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日本板硝子株式会社
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Application filed by 日本板硝子株式会社 filed Critical 日本板硝子株式会社
Priority to JP2018513198A priority Critical patent/JP6864672B2/en
Publication of WO2017183660A1 publication Critical patent/WO2017183660A1/en

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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
    • D02G3/26—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre with characteristics dependent on the amount or direction of twist
    • D02G3/28—Doubled, plied, or cabled threads
    • 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
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/418—Cyclic amides, e.g. lactams; Amides of oxalic acid
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
    • 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
    • D06M15/55—Epoxy resins
    • 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
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G1/00—Driving-belts
    • F16G1/06—Driving-belts made of rubber
    • F16G1/08—Driving-belts made of rubber with reinforcement bonded by the rubber

Definitions

  • the present invention relates to a rubber reinforcing cord and a rubber product using the same.
  • Rubber reinforcing cords formed from tough fibers are widely used as reinforcing materials for rubber products that repeatedly receive bending stresses such as rubber belts and tires. Since the rubber reinforcing cord is used as a tensile body for enhancing the dimensional stability of the rubber product, it requires a high tensile strength.
  • the manufacturing process of the rubber reinforcing cord generally includes a process of applying a treatment agent containing resorcin, formaldehyde, rubber latex (RFL) to the fiber and drying it (RFL process process). Further, as the treating agent applied to the fiber, a treating agent containing a material that is crosslinked by heat treatment and not containing a resorcin-formaldehyde condensate may be used. With the coating formed by such a treatment agent, the rubber reinforcing cord can improve the adhesion with the matrix rubber when embedded in the rubber composition (matrix rubber) constituting the rubber product.
  • Examples of fibers used in rubber reinforcing cords include aramid fibers.
  • Aramid fibers are generally fibers having high strength and high elastic modulus, and are widely used as reinforcing cords for rubber belts for power transmission.
  • Patent Documents 1 to 3 propose rubber reinforcing cords obtained by treating aramid fibers using a treatment agent containing RFL.
  • Patent Document 4 proposes a rubber reinforcing cord obtained by treating an aramid fiber with a treating agent that contains a material that is crosslinked by heat treatment and does not contain a resorcin-formaldehyde condensate.
  • JP-A-8-100300 JP 2005-517097 Publication JP 2010-95814 A Japanese Patent No. 4217058
  • polyparaphenylene terephthalamide fibers known as para-type aramid fibers have a problem that the tensile strength is greatly reduced by heat treatment when the treatment agent is dried. In particular, the tensile strength is greatly reduced by heating during the RFL treatment process.
  • the amount of heat applied during the RFL treatment process is suppressed to a low level, the decrease in tensile strength can be suppressed to a small level, but this causes a problem that sufficient adhesive strength between the matrix rubber and the rubber reinforcing cord cannot be obtained.
  • the amount of heat applied can be reduced compared with the case of using a treatment agent that contains RFL, but it is still a matrix rubber.
  • one of the objects of the present invention is to obtain a rubber reinforcing cord that contains polyparaphenylene terephthalamide fiber as a reinforcing fiber and that has both high tensile strength and high adhesive strength. Further, another object of the present invention is to provide a high strength rubber reinforced by such a rubber reinforcing cord and having a high tensile strength and a high adhesive strength between the matrix rubber and the rubber reinforcing cord. Is to provide products.
  • the present inventor used polyparaphenylene terephthalamide fiber as a reinforcing fiber, and in the case of a rubber reinforcing cord obtained by forming a film using a treating agent on the surface of the fiber,
  • the ratio of the liquid components remaining in the cord affects the tensile strength of the rubber reinforcing cord and the adhesive strength of the rubber reinforcing cord to the matrix rubber.
  • the present invention has led to the following rubber reinforcing cords of the present invention that can be located and have both high tensile strength and high adhesive strength.
  • the present invention is a rubber reinforcing cord for reinforcing a rubber product
  • the rubber reinforcing cord includes at least one strand,
  • the strand includes at least one filament bundle, and a first coating provided to cover at least a part of the surface of the filament bundle,
  • the filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments
  • the first coating includes a rubber component and a crosslinking agent
  • the rubber reinforcing cord further includes a liquid component, and the content of the liquid component in the rubber reinforcing cord is in the range of 0.1 to 2.0 mass%.
  • the present invention also provides a rubber product reinforced with the rubber reinforcing cord of the present invention.
  • a cord for rubber reinforcement that achieves both high tensile strength and high adhesive strength with matrix rubber is provided. it can.
  • the rubber product of the present invention is reinforced with such a rubber reinforcing cord, it is possible to realize a high tensile strength and a high adhesive strength between the matrix rubber and the rubber reinforcing cord.
  • the rubber reinforcing cord of the present embodiment is a cord for reinforcing a rubber product.
  • the rubber reinforcing cord includes at least one strand.
  • the strand includes at least one filament bundle and a first coating provided so as to cover at least a part of the surface of the filament bundle.
  • the filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments.
  • the first coating contains a rubber component and a crosslinking agent.
  • the rubber reinforcing cord of this embodiment further includes a liquid component, and the content of the liquid component in the rubber reinforcing cord is in the range of 0.1 to 2.0% by mass.
  • the liquid component contained in the rubber reinforcing cord is, for example, a solvent contained in an aqueous treatment agent (first aqueous treatment agent for coating) used for producing the first coating, or moisture contained in the filament itself. It is constituted by the remaining etc.
  • the filament bundle constituting the strand includes a plurality of filaments.
  • the filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments.
  • “the filament bundle is substantially composed of polyparaphenylene terephthalamide fiber filament” means that the filament bundle includes filaments other than the polyparaphenylene terephthalamide fiber filament to such an extent that the effect of the invention is not greatly affected. It means that it may be included.
  • the filament bundle may include filaments other than polyparaphenylene terephthalamide fiber filaments at a ratio of 10% or less (for example, 5% or less or 1% or less) in the cross-sectional area of the filament bundle.
  • polyparaphenylene terephthalamide fiber examples include “Twaron” manufactured by Teijin Limited and “Kevlar” manufactured by Toray DuPont Co., Ltd.
  • filament other than the polyparaphenylene terephthalamide fiber filament a filament of a fiber generally used as a reinforcing fiber of a rubber reinforcing cord can be used.
  • the filament bundle may consist only of polyparaphenylene terephthalamide fibers.
  • the number of filaments contained in the filament bundle is not particularly limited.
  • the filament bundle can include, for example, a range of 200 to 2000 filaments.
  • the surface of the polyparaphenylene terephthalamide fiber filament contained in the filament bundle is subjected to pretreatment for increasing the adhesive strength.
  • a preferred example of the pretreatment agent is a compound containing at least one functional group selected from the group consisting of an epoxy group and an amino group.
  • the pretreatment agent include aminosilane, epoxysilane, novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin, bisphenol AD type epoxy resin, glycidylamine type epoxy resin, and the like.
  • Specific examples include Nagase ChemteX's Denacol series, DIC's Epicron series, and Mitsubishi Chemical's Epicoat series.
  • a polyurethane resin and an isocyanate compound can be similarly used as a pretreatment agent.
  • a pretreatment agent a treatment agent containing at least one selected from the group consisting of an epoxy resin, a urethane resin, and an isocyanate compound may be used.
  • a polyparaphenylene terephthalamide fiber filament whose surface is pretreated, it is possible to enhance the adhesion between the matrix rubber and the rubber reinforcing cord.
  • the number of filament bundles included in the rubber reinforcing cord is not limited, and may be one or plural.
  • the filament bundle may be a bundle of a plurality of filament bundles.
  • each of the plurality of filament bundles may be twisted or may not be twisted. Moreover, it may be twisted in a state where a plurality of filament bundles are combined, or may not be twisted.
  • the first coating is provided so as to cover at least a part of the surface of the filament bundle.
  • the first coating may be provided directly on the surface of the filament bundle, or through another layer (for example, a coating (for example, the resin layer) formed by the above-described filament pretreatment).
  • the surface of the filament bundle may be covered.
  • the first coating is formed by supplying a first aqueous coating agent for coating described later to at least a part of the surface of the filament bundle and drying it by heat treatment.
  • the supply of the first aqueous treatment agent to the surface of the filament bundle may be performed by, for example, impregnating the filament bundle with the first aqueous treatment agent for coating, or at least part of the surface of the filament bundle with the first aqueous coating solution. It can be carried out by applying a treatment agent.
  • moisture content which the filament itself has, and the solvent (for example, water) of an aqueous processing agent are substantially removed by the heat processing in this case.
  • the first coating contains a rubber component.
  • the rubber component preferably contains at least one selected from the group consisting of nitrile rubber, hydrogenated nitrile rubber, carboxyl-modified nitrile rubber, and carboxyl-modified hydrogenated nitrile rubber.
  • the first coating may contain only one type of rubber as a rubber component, or may contain a plurality of types. These rubbers are preferable in that they are less swelled by oil and excellent in oil resistance.
  • the term “nitrile rubber” means a nitrile rubber (acrylonitrile-butadiene copolymer rubber) that is not hydrogenated or carboxyl-modified unless otherwise specified.
  • the iodine value of the hydrogenated nitrile rubber is usually 120 or less, and may be 100 or less, for example.
  • An example hydrogenated nitrile rubber has an iodine value in the range of 0-50.
  • the first film may contain other rubber in addition to the rubber.
  • examples of other rubbers include butadiene / styrene copolymers, dicarboxylated butadiene / styrene copolymers, vinylpyridine / butadiene / styrene copolymers, chloroprene rubber, butadiene rubber, and chlorosulfonated polyethylene.
  • the first film further contains a cross-linking agent.
  • the rubber reinforcing cord of the present embodiment can improve the adhesion with the matrix rubber.
  • crosslinking agents include quinonedioxime crosslinking agents such as P-quinonedioxime, methacrylate crosslinking agents such as lauryl methacrylate and methyl methacrylate, DAF (diallyl fumarate), DAP (diallyl phthalate), TAC (Triallyl cyanurate) and TAIC (triallyl isocyanurate) and other allyl crosslinking agents, bismaleimide, phenylmaleimide and maleimide crosslinking agents such as N, N'-m-phenylenedimaleimide, aromatic or aliphatic Organic diisocyanates, polyisocyanates, blocked isocyanates, blocked polyisocyanates, aromatic nitroso compounds, sulfur, and peroxides are included.
  • crosslinking agents may be used alone or in combination of two or more. These crosslinking agents are selected in consideration of the type of rubber contained in the first coating, the type of matrix rubber in which the rubber reinforcing cord is embedded, and the like. In addition, it is preferable that these crosslinking agents are used in the form of an aqueous dispersion so that the crosslinking agent is present uniformly in the aqueous treatment agent for producing the first coating film.
  • the crosslinking agent may be at least one selected from the group consisting of a maleimide crosslinking agent, an organic diisocyanate, and an aromatic nitroso compound.
  • crosslinking agents it is preferable to use at least one selected from the group consisting of maleimide crosslinking agents and polyisocyanates.
  • maleimide crosslinking agents 4,4'-bismaleimide diphenylmethane is preferably used because it has good stability when dispersed in water, has a high crosslinking effect, and has high heat resistance after crosslinking.
  • the maleimide-based crosslinking agent and polyisocyanate can specifically enhance the adhesion between the reinforcing cord and the matrix rubber by combining with the rubber latex.
  • a combination of a latex of a carboxyl-modified hydrogenated nitrile rubber and a maleimide-based crosslinking agent is preferable because the adhesion can be further improved.
  • the first film may further contain a filler.
  • fillers include fine particles of covalently bonded compounds such as carbon black and silica, fine particles of hardly soluble salts, fine particles of metal oxide, fine particles of metal hydroxide, fine particles of complex metal oxide salts such as talc. included. Among these, at least one selected from the group consisting of carbon black and silica is preferable.
  • the average particle size of carbon black is preferably in the range of 5 to 300 nm, for example, in the range of 100 to 200 nm, and more preferably in the range of 130 to 170 nm.
  • the average particle diameter of silica is preferably in the range of 5 to 200 nm, for example in the range of 7 to 100 nm, and more preferably in the range of 7 to 30 nm.
  • the average particle diameter is a value obtained by measuring the particle diameter of 50 or more particles using a transmission electron microscope and dividing the total of the particle diameters by the number of measured particles. When the particles were not spherical, the average of the longest diameter and the shortest diameter of each particle was taken as the particle size.
  • the filler has an effect of improving the properties such as the tensile strength and tear strength of the coating by being dispersed in the rubber.
  • the filler also has the effect of improving the adhesive strength by increasing the cohesive strength of the adhesive component between the fiber and the coating and between the coating and the matrix rubber.
  • the first coating preferably contains no resorcin-formaldehyde condensate. In that case, when producing the first coating, it is not necessary to use a substance with a large environmental load such as formaldehyde and ammonia, so that no environmental measures are required for the operator. However, the first film may contain a resorcin-formaldehyde condensate.
  • the first coating film further includes a filler and further other components (for example, a metal oxide other than the metal oxide added as the filler or a resin). May be.
  • the contents of the rubber component and the crosslinking agent in the first coating are not particularly limited.
  • the content of the rubber component in the first coating can be set to 50 to 90% by mass, for example.
  • the content of the crosslinking agent in the first coating can be in the range of 10 to 50% by mass, for example.
  • the mass of the first coating film provided on at least the surface of the filament bundle is not particularly limited and may be adjusted as appropriate, but it is preferably provided so as to be in the range of 5 to 35% of the mass of the filament bundle.
  • the mass of the first coating may be in the range of 10 to 25% of the mass of the filament bundle, or may be in the range of 12 to 20% by mass.
  • problems such as a decrease in the dimensional stability of the rubber reinforcing cord in the rubber product and a decrease in the elastic modulus of the rubber reinforcing cord may occur.
  • the mass of the first coating is too small, the strands are likely to fray or the function of protecting the fibers by the first coating is reduced, and as a result, the life of the rubber product may be reduced. .
  • the rubber reinforcing cord of the present embodiment may further include a second coating formed on the first coating.
  • the treatment agent for forming the second coating may be the same as or different from the first aqueous treatment agent for coating.
  • the number of twists of the rubber reinforcing cord of the present embodiment is not particularly limited.
  • the number of twists (hereinafter sometimes referred to as the lower twist) applied to one strand is, for example, in the range of 20 to 160 times / m, in the range of 30 to 120 times / m, or in the range of 40 to 100 times / m. It may be a range.
  • the number of twists (hereinafter sometimes referred to as upper twists) applied to the plurality of strands is also in the range of, for example, 20 to 160 times / m, 30 to 120 times / m, or 40 to 100. It may be in the range of times / m.
  • the Lang twist may be the same as the lower twist direction and the upper twist direction, and the Moro twist may be the reverse of the lower twist direction and the upper twist direction. There is no limitation in the direction of twist, and it may be the S direction or the Z direction.
  • the content of the liquid component in the rubber reinforcing cord of the present embodiment is in the range of 0.1 to 2.0% by mass.
  • this liquid component is a residual solvent such as a solvent (for example, water) contained in an aqueous treatment agent used when a film is formed or moisture contained in the filament itself.
  • the second coating is produced when the rubber reinforcing cord of the present embodiment further includes the second coating.
  • the polyparaphenylene terephthalamide fiber is pulled by adjusting the amount of heat so that the liquid component remains in the rubber reinforcing cord within the range of 0.1 to 2.0% by mass.
  • the content of the liquid component is less than 0.1% by mass, that is, the heat treatment at the time of producing the first film, and further the heat treatment at the time of producing the second film are contained in the solvent of the treatment agent for producing the film and the fiber
  • the tensile strength of the polyparaphenylene terephthalamide fiber is lowered, and as a result, the tensile strength of the rubber reinforcing cord is lowered.
  • the content of the liquid component exceeds 2.0% by mass, a sufficient amount of heat has not been applied to the coating so that sufficient adhesive strength with the matrix rubber can be realized. It is not possible to obtain a rubber reinforcing cord capable of realizing sufficient adhesive strength.
  • the content of the liquid component in the rubber reinforcing cord is preferably 0.2 to 1.5% by mass, More preferably, the content is 3 to 1.3% by mass.
  • the “content ratio of the liquid component in the rubber reinforcing cord” specified in the present invention is a value obtained as follows. A 5 m long cord is taken as a sample from the rubber reinforcing cord, the sample is measured with an electronic balance, and this value is taken as the mass A of the cord. The sample was placed in a dryer heated to 150 ° C. for 30 minutes to remove the solvent in the sample. Was the mass (AB) of the liquid component contained in the cord. The percentage ( ⁇ (AB) / A ⁇ ⁇ 100) of the mass (AB) of the liquid component contained in the cord with respect to the mass A of the cord is defined as the liquid component content (%).
  • the solvent of the treatment agent is water
  • heat treatment is performed at 150 ° C. for 30 minutes in order to completely remove water from the sample, but a solvent other than water is used. If it is, an appropriate heating temperature and heating time may be set so that the solvent can be completely removed.
  • the rubber reinforcing cord further includes a second coating provided on the first coating
  • heat treatment is also performed when the second coating is produced. Therefore, it is preferable that the heat treatment for producing the second coating is also performed within a range that prevents a decrease in tensile strength and adhesive strength.
  • the second coating is applied to the liquid component in the rubber reinforcing cord. In some cases, a liquid such as a remaining solvent is contained. Therefore, in the case of the rubber reinforcing cord including the second coating, it is preferable that the content of the liquid component in the rubber reinforcing cord is in the range of 0.5 to 2.0% by mass.
  • a plurality of filaments are bundled to produce a filament bundle, and further an aqueous treatment agent (first aqueous treatment agent for coating) used for producing the first coating is prepared.
  • the first aqueous coating agent for coating is supplied to at least a part of the surface of the filament bundle.
  • heat treatment is performed to remove the solvent in the first aqueous coating agent.
  • 1000 filaments are aligned to form one bundle, and the surface of the bundle is coated or impregnated with the first aqueous coating agent for coating.
  • the solvent in the first aqueous coating agent for coating is removed by heat treatment.
  • the filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments.
  • the first film is formed on at least a part of the surface of the filament bundle by the above process.
  • the method for supplying the first aqueous coating agent for coating to at least a part of the surface of the filament bundle is not limited.
  • the first aqueous coating agent for coating may be applied to the surface of the filament bundle.
  • the bundle may be immersed in the first aqueous coating agent for coating.
  • the conditions of the heat treatment for removing the solvent of the first aqueous coating agent for coating are not particularly limited, but the content of the liquid component of the cord obtained after the heat treatment is 0.1 to 2.0% by mass.
  • the processing temperature and processing time are adjusted appropriately.
  • the treatment temperature and treatment time are appropriately adjusted so that the content of the liquid component of the cord obtained after the heat treatment is 0.2 to 1.5% by mass, more preferably 0.3 to 1.3% by mass. It is to be.
  • the processing temperature is preferably 220 ° C. or lower, for example.
  • the treatment time is not particularly limited, and in consideration of the heat treatment temperature, the amount of heat applied is within the range specified in this embodiment by the liquid component content in the completed rubber reinforcing cord (0.1 to 2.0 mass). %) May be adjusted as appropriate so that the amount of heat can be realized.
  • the filament bundle on which the first film is formed is usually twisted in one direction.
  • the twisting direction may be the S direction or the Z direction. Since the number of filaments contained in the filament bundle and the number of twists of the filament bundle have been described above, description thereof will be omitted. In this way, the rubber reinforcing cord of this embodiment can be manufactured.
  • a plurality of bundles of filaments on which the first film is formed may be formed, and the plurality of bundles of filaments may be bundled to add an upper twist.
  • the direction of the upper twist may be the same as or different from the direction of twist of the filament bundle (the direction of the lower twist).
  • a plurality of filament bundles on which the first film is formed may be formed, and a twist may be added to a bundle of a plurality of filament bundles without giving a twist to each filament bundle.
  • the first film may be formed after twisting the filament bundle.
  • the type, number, and number of twists of the filament are as described above.
  • the first bundle of aqueous coating agent is applied or impregnated into the filament bundle, and then the bundle is twisted in one direction to form a rubber reinforcing cord.
  • the second film When the second film is formed on the first film, a treatment agent for forming the second film is applied on the first film, and the solvent in the treatment agent is removed.
  • the second film may be formed by The type of the second coating can be appropriately selected according to the matrix rubber of the rubber product to which the rubber reinforcing cord is applied, and is particularly preferably selected from the viewpoint of improving adhesiveness.
  • the conditions of the heat treatment for removing the solvent of the second coating treatment agent are not particularly limited, but the content of the liquid component of the cord obtained after the heat treatment is 0.5 to 2.0% by mass. It is preferable to appropriately adjust the treatment temperature and the treatment time.
  • the first aqueous coating agent for coating may include a latex of at least one rubber selected from the group consisting of nitrile rubber, hydrogenated nitrile rubber, carboxyl-modified nitrile rubber, and carboxyl-modified hydrogenated nitrile rubber. preferable.
  • the aqueous treatment agent may contain only one of these rubber latexes, or may contain a plurality of these rubber latexes.
  • the first aqueous coating agent for coating may contain other rubber latex in addition to the above rubber latex.
  • Other rubber latex examples include butadiene / styrene copolymer latex, dicarboxylated butadiene / styrene copolymer latex, vinylpyridine / butadiene / styrene terpolymer latex, chloroprene latex, butadiene latex, and chlorosulfonated polyethylene latex. included.
  • the aqueous treatment agent may contain a plurality of these rubber latexes.
  • the first aqueous coating agent for coating further contains a crosslinking agent. Since the crosslinking agent contained in the first aqueous coating agent for coating is the same as that described above as the crosslinking agent contained in the first coating, description thereof is omitted here. In addition, it is preferable to use a crosslinking agent in the form of an aqueous dispersion in order to make it exist uniformly in an aqueous processing agent.
  • the first aqueous coating agent for coating may further contain a filler. Since the filler contained in the first aqueous coating agent for coating is the same as that described above as the filler contained in the first coating, description thereof is omitted here.
  • the first aqueous treatment agent for coating does not contain a resorcin-formaldehyde condensate.
  • the first aqueous coating agent for coating may contain a resorcin-formaldehyde condensate.
  • the first aqueous coating agent for coating may contain a filler and further other components in addition to the rubber latex and the crosslinking agent.
  • the first aqueous coating agent for coating may contain a resin, a plasticizer, an anti-aging agent, a stabilizer, a metal oxide other than the metal oxide added as the filler, and the like.
  • the aqueous treatment agent may not contain a resin.
  • the rubber product of the present embodiment is a rubber product reinforced with the rubber reinforcing cord of the present embodiment.
  • rubber products of the present embodiment include automobile and bicycle tires, transmission belts, and the like.
  • the transmission belt include a meshing transmission belt and a friction transmission belt.
  • the meshing transmission belt include a toothed belt represented by an automobile timing belt and the like.
  • the friction transmission belt include a flat belt, a round belt, a V belt, a V-ribbed belt, and the like. That is, the rubber product of the present embodiment may be a toothed belt, a flat belt, a round belt, a V belt, or a V-ribbed belt.
  • the rubber product of the present embodiment is formed by embedding the rubber reinforcing cord of the present embodiment in a rubber composition (matrix rubber).
  • the method for embedding the rubber reinforcing cord in the matrix rubber is not particularly limited, and a known method may be applied.
  • the rubber reinforcing cord of this embodiment is embedded in the rubber product (for example, rubber belt) of this embodiment. Therefore, the rubber product of the present embodiment has high bending fatigue resistance. Therefore, the rubber product of the present embodiment is particularly suitable for applications such as a timing belt for a vehicle engine and a belt for driving an auxiliary machine for a vehicle.
  • the rubber contained in the rubber composition in which the rubber reinforcing cord of the present embodiment is embedded is not particularly limited, and may be chloroprene rubber, chlorosulfonated polyethylene rubber, ethylene propylene rubber, hydrogenated nitrile rubber, or the like.
  • the hydrogenated nitrile rubber may be a hydrogenated nitrile rubber in which a zinc acrylate derivative (for example, zinc methacrylate) is dispersed.
  • At least one rubber selected from hydrogenated nitrile rubber and hydrogenated nitrile rubber in which a zinc acrylate derivative is dispersed is preferable from the viewpoint of water resistance and oil resistance.
  • the matrix rubber may further contain a carboxyl-modified hydrogenated nitrile rubber.
  • the toothed belt 1 shown in FIG. 1 includes a belt main body 11 and a plurality of rubber reinforcing cords 12.
  • the belt body 11 includes a belt portion 13 and a plurality of tooth portions 14 protruding from the belt portion 13 at regular intervals.
  • the rubber reinforcing cord 12 is embedded in the belt portion 13 so as to be parallel to the longitudinal direction of the belt portion 13.
  • the rubber reinforcing cord 12 is the rubber reinforcing cord of the present embodiment.
  • the solid content of the first aqueous coating agent for coating was 20% by mass, and the mass of the first coating was 20% of the mass of the filament bundle.
  • the “liquid component content” was adjusted by changing the heat treatment time.
  • the filament bundle with the first coating produced in this manner is twisted into a Z twist at a rate of 40 turns / m, and two of them are bundled and twisted into a Z twist at a rate of 100 turns / m.
  • a rubber reinforcing cord was obtained. About the obtained rubber
  • the measuring method of the content rate of a liquid component, tensile strength, and adhesive strength is as follows.
  • a canvas, a rubber reinforcing cord, and a matrix rubber sheet were stacked in this order, and pressed at 160 ° C. for 30 minutes to prepare a test piece for an adhesive strength test.
  • the dimensions of the test piece were 25 mm in width, 150 mm in length, and 3 mm in thickness.
  • the length direction of the rubber reinforcing cord was substantially parallel to the length direction of the test piece.
  • the matrix rubber a material mainly composed of hydrogenated nitrile rubber having the composition shown in Table 2 was used. Next, the cord and the matrix rubber were each gripped, one was fixed, the other was peeled off in the length direction of the rubber reinforcing cord, and the strength per 25 mm width was measured.
  • the content of the liquid component in the rubber reinforcing cords of Examples 1 to 10 was in the range of 0.1 to 2.0% by mass.
  • the liquid component content was less than 0.1% by mass.
  • the rubber reinforcing cords of Comparative Examples 2 to 6 the liquid component content exceeded 2.0 mass%.
  • the rubber reinforcing cord of Comparative Example 1 was subjected to an excessive heat treatment exceeding the range of the heat treatment assumed for obtaining the rubber reinforcing cord of the present invention.
  • the rubber reinforcing cord was subjected to an insufficient heat treatment less than the range of heat treatment envisaged for obtaining the rubber reinforcing cord of the present invention.
  • the adhesive strength was 150 N / 25 mm or more
  • the peeling interface was partially damaged by rubber, and when it was less than 150 N / 25 mm, the interface was in the vicinity of the first coating. From this result, it was confirmed that the ratio of the liquid component remaining in the cord after the formation of the first coating (mainly the solvent for the first aqueous coating agent) has a correlation with the tensile strength and the adhesive strength. It was.
  • Examples 11 to 20 and Comparative Examples 7 to 11 ⁇ Manufacture of rubber reinforcing cord>
  • a first coating is formed on the surface of the filament bundle, and the filament bundle with the first coating is Z-twisted at a rate of 40 times / m.
  • a cord was obtained by twisting the bottom and bundling two of them and twisting them into a Z twist at a rate of 100 turns / m.
  • a second coating agent having the composition shown in Table 5 below was applied onto the cord after twisting and dried to form a second coating.
  • the rubber reinforcing cords of Examples 7 to 11 were used.
  • the second film was 10% by mass with respect to the cord after the upper twist.
  • the drying of the second coating treatment agent was performed at a treatment temperature of 100 ° C. and a treatment time of 2 minutes.
  • the content of the liquid component after forming the second coating is in the range of 0.5 to 1.9% by mass as shown in Table 6, and the second coating treatment is applied to the liquid component of the rubber reinforcing cord. It is thought that the solvent of the agent is also included.
  • the content ratio of the liquid component after the formation of the second coating satisfied the range of 0.5 to 2.0% by mass.
  • the liquid component content exceeded 2 mass%.
  • the rubber reinforcing cords of Comparative Examples 7 to 11 were subjected to insufficient heat treatment that did not satisfy the range of heat treatment envisaged for obtaining the rubber reinforcing cord of the present invention.
  • the cord for reinforcing rubber according to the present invention can realize high adhesive strength with a matrix rubber and high tensile strength, and can be applied to reinforcement of various rubber products.
  • it can be suitably used as a reinforcing cord for a timing belt or the like that requires a high level of heat resistance and bending fatigue resistance.
  • the rubber product of this invention can endure a high load, it is applicable to various uses.

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Abstract

A rubber-reinforcing cord according to the present invention is a rubber-reinforcing cord for reinforcing a rubber product and includes at least one strand. The strand includes at least one filament bundle and a first film that is provided so as to cover at least a portion of the surface of the filament bundle. The filament bundle is substantially formed of polyparaphenylene terephthalamide fiber filaments. The first film contains a rubber component and a crosslinking agent. The rubber-reinforcing cord further contains a liquid component, and the liquid-component content in the rubber-reinforcing cord is in the range of 0.1 to 2.0 mass%.

Description

ゴム補強用コード及びそれを用いたゴム製品Rubber reinforcing cord and rubber product using the same
　本発明は、ゴム補強用コードと、それを用いたゴム製品とに関する。 The present invention relates to a rubber reinforcing cord and a rubber product using the same.
　ゴムベルト及びタイヤなどの屈曲応力を繰り返し受けるゴム製品の補強材として、強靱な繊維を用いて形成されるゴム補強用コードが広く用いられている。ゴム補強用コードは、ゴム製品の寸法安定性を高めるための抗張体として用いられるので、高い引張強度を必要とする。 Rubber reinforcing cords formed from tough fibers are widely used as reinforcing materials for rubber products that repeatedly receive bending stresses such as rubber belts and tires. Since the rubber reinforcing cord is used as a tensile body for enhancing the dimensional stability of the rubber product, it requires a high tensile strength.
　ゴム補強用コードの製造工程は、一般に、レゾルシン・ホルムアルデヒド・ゴムラテックス（ＲＦＬ）を含む処理剤を繊維に塗布して乾燥させる工程（ＲＦＬ処理工程）を含む。また、繊維に塗布する処理剤としては、熱処理によって架橋される材料を含み、かつレゾルシン－ホルムアルデヒド縮合物を含まない処理剤が用いられることもある。このような処理剤によって形成される被膜により、ゴム補強用コードは、ゴム製品を構成するゴム組成物（マトリックスゴム）に埋め込まれた際のマトリックスゴムとの接着性を向上させることができる。 The manufacturing process of the rubber reinforcing cord generally includes a process of applying a treatment agent containing resorcin, formaldehyde, rubber latex (RFL) to the fiber and drying it (RFL process process). Further, as the treating agent applied to the fiber, a treating agent containing a material that is crosslinked by heat treatment and not containing a resorcin-formaldehyde condensate may be used. With the coating formed by such a treatment agent, the rubber reinforcing cord can improve the adhesion with the matrix rubber when embedded in the rubber composition (matrix rubber) constituting the rubber product.
　ゴム補強用コードに用いられる繊維として、例えばアラミド繊維が挙げられる。アラミド繊維は、一般に、高強度及び高弾性率を有する繊維であり、動力伝達用のゴムベルトの補強用コードとして広く用いられている。ＲＦＬを含む処理剤を用いてアラミド繊維を処理することによって得られるゴム補強用コードは、例えば特許文献１～３で提案されている。また、熱処理によって架橋される材料を含み、かつレゾルシン－ホルムアルデヒド縮合物を含まない処理剤を用いてアラミド繊維を処理することによって得られるゴム補強用コードは、例えば特許文献４で提案されている。 Examples of fibers used in rubber reinforcing cords include aramid fibers. Aramid fibers are generally fibers having high strength and high elastic modulus, and are widely used as reinforcing cords for rubber belts for power transmission. For example, Patent Documents 1 to 3 propose rubber reinforcing cords obtained by treating aramid fibers using a treatment agent containing RFL. Further, for example, Patent Document 4 proposes a rubber reinforcing cord obtained by treating an aramid fiber with a treating agent that contains a material that is crosslinked by heat treatment and does not contain a resorcin-formaldehyde condensate.
特開平８－１００３７０号公報JP-A-8-100300 特表２００５－５１７０９７号公報JP 2005-517097 Publication 特開２０１０－９５８１４号公報JP 2010-95814 A 特許第４２１７０５８号Japanese Patent No. 4217058
　しかし、アラミド繊維のうち、パラ型アラミド繊維として知られるポリパラフェニレンテレフタルアミド繊維は、処理剤を乾燥させる際の熱処理によって引張強度が大きく低下するという問題を有する。特に、ＲＦＬ処理工程時の加熱により、引張強度が大きく低下する。一方、ゴム補強用コードとマトリックスゴムとの間の良好な接着強度を得るためには、ＲＦＬ処理工程時の熱処理において、ＲＦＬの反応のために十分な熱量を与える必要がある。したがって、ＲＦＬ処理工程時に付与する熱量を小さく抑えれば、引張強度の低下は小さく抑えることができるものの、そうするとマトリックスゴムとゴム補強用コードとの十分な接着強度が得られなくなるという問題が生じる。熱処理によって架橋される材料を含み、かつレゾルシン－ホルムアルデヒド縮合物を含まない処理剤を用いた場合は、ＲＦＬを含む処理剤を用いる場合よりも付与する熱量を低減できる場合もあるものの、それでもマトリックスゴムとゴム補強用コードとの十分な接着強度を得るために必要な熱量を付与した場合は、引張強度の低下は避けられない。このように、ポリパラフェニレンテレフタルアミド繊維を用いて、高い引張強度と高い接着強度とを両立するゴム補強用コードを得ることは困難であった。 However, among the aramid fibers, polyparaphenylene terephthalamide fibers known as para-type aramid fibers have a problem that the tensile strength is greatly reduced by heat treatment when the treatment agent is dried. In particular, the tensile strength is greatly reduced by heating during the RFL treatment process. On the other hand, in order to obtain good adhesion strength between the rubber reinforcing cord and the matrix rubber, it is necessary to give a sufficient amount of heat for the RFL reaction in the heat treatment during the RFL treatment process. Therefore, if the amount of heat applied during the RFL treatment process is suppressed to a low level, the decrease in tensile strength can be suppressed to a small level, but this causes a problem that sufficient adhesive strength between the matrix rubber and the rubber reinforcing cord cannot be obtained. In the case of using a treatment agent that contains a material that is crosslinked by heat treatment and does not contain a resorcinol-formaldehyde condensate, the amount of heat applied can be reduced compared with the case of using a treatment agent that contains RFL, but it is still a matrix rubber. When a heat amount necessary for obtaining a sufficient adhesive strength between the rubber reinforcing cord and the rubber reinforcing cord is applied, a decrease in tensile strength is inevitable. Thus, it has been difficult to obtain a rubber reinforcing cord having both high tensile strength and high adhesive strength using polyparaphenylene terephthalamide fiber.
　そこで、本発明の目的の一つは、ポリパラフェニレンテレフタルアミド繊維を補強用の繊維として含み、かつ高い引張強度と高い接着強度とを両立するゴム補強用コードを得ることである。さらに、本発明の別の目的の一つは、そのようなゴム補強用コードによって補強された、高い引張強度、さらにマトリックスゴムとゴム補強用コードとの高い接着強度とを有する、高強度のゴム製品を提供することである。 Therefore, one of the objects of the present invention is to obtain a rubber reinforcing cord that contains polyparaphenylene terephthalamide fiber as a reinforcing fiber and that has both high tensile strength and high adhesive strength. Further, another object of the present invention is to provide a high strength rubber reinforced by such a rubber reinforcing cord and having a high tensile strength and a high adhesive strength between the matrix rubber and the rubber reinforcing cord. Is to provide products.
　本発明者は、鋭意研究の末、ポリパラフェニレンテレフタルアミド繊維を補強用の繊維として用い、この繊維の表面に処理剤を用いて被膜を形成して得られるゴム補強用コードの場合、ゴム補強用コードに残存する液体成分（処理剤の溶媒及び繊維に含まれる水分など）の割合が、ゴム補強用コードの引張強度と、ゴム補強用コードのマトリックスゴムに対する接着強度とに影響を及ぼすことを突き止め、高い引張強度と高い接着強度とを両立することができる以下の本発明のゴム補強用コードに至った。 As a result of intensive research, the present inventor used polyparaphenylene terephthalamide fiber as a reinforcing fiber, and in the case of a rubber reinforcing cord obtained by forming a film using a treating agent on the surface of the fiber, The ratio of the liquid components remaining in the cord (such as the solvent of the processing agent and moisture contained in the fiber) affects the tensile strength of the rubber reinforcing cord and the adhesive strength of the rubber reinforcing cord to the matrix rubber. The present invention has led to the following rubber reinforcing cords of the present invention that can be located and have both high tensile strength and high adhesive strength.
　本発明は、ゴム製品を補強するためのゴム補強用コードであって、
　前記ゴム補強用コードは、少なくとも１つのストランドを備え、
　前記ストランドは、少なくとも１つのフィラメント束と、前記フィラメント束の少なくとも表面の一部を覆うように設けられた第１の被膜と、
を含んでおり、
　前記フィラメント束は、実質的にポリパラフェニレンテレフタルアミド繊維フィラメントからなり、
　前記第１の被膜は、ゴム成分及び架橋剤を含み、
　前記ゴム補強用コードは液体成分をさらに含んでおり、前記ゴム補強用コードにおける前記液体成分の含有率が０．１～２．０質量％の範囲内である。 The present invention is a rubber reinforcing cord for reinforcing a rubber product,
The rubber reinforcing cord includes at least one strand,
The strand includes at least one filament bundle, and a first coating provided to cover at least a part of the surface of the filament bundle,
Contains
The filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments,
The first coating includes a rubber component and a crosslinking agent,
The rubber reinforcing cord further includes a liquid component, and the content of the liquid component in the rubber reinforcing cord is in the range of 0.1 to 2.0 mass%.
　また、本発明は、上記本発明のゴム補強用コードで補強されたゴム製品を提供する。 The present invention also provides a rubber product reinforced with the rubber reinforcing cord of the present invention.
　本発明によれば、補強用の繊維としてポリパラフェニレンテレフタルアミド繊維が用いられている場合であっても、高い引張強度と、マトリックスゴムとの高い接着強度とを両立するゴム補強用コードを提供できる。また、本発明のゴム製品は、このようなゴム補強用コードで補強されているので、高い引張強度、さらにマトリックスゴムとゴム補強用コードとの高い接着強度とを実現できる。 According to the present invention, even when polyparaphenylene terephthalamide fiber is used as a reinforcing fiber, a cord for rubber reinforcement that achieves both high tensile strength and high adhesive strength with matrix rubber is provided. it can. In addition, since the rubber product of the present invention is reinforced with such a rubber reinforcing cord, it is possible to realize a high tensile strength and a high adhesive strength between the matrix rubber and the rubber reinforcing cord.
本発明のゴム製品の一例を模式的に示す一部分解斜視図である。It is a partial exploded perspective view showing typically an example of the rubber product of the present invention.
　以下、本発明の実施形態について具体的に説明する。 Hereinafter, embodiments of the present invention will be specifically described.
［ゴム補強用コード］
　本実施形態のゴム補強用コードは、ゴム製品を補強するためのコードである。このゴム補強用コードは、少なくとも１つのストランドを備えている。このストランドは、少なくとも１つのフィラメント束と、フィラメント束の少なくとも表面の一部を覆うように設けられた第１の被膜と、を含んでいる。フィラメント束は、実質的にポリパラフェニレンテレフタルアミド繊維フィラメントからなる。第１の被膜は、ゴム成分及び架橋剤を含む。本実施形態のゴム補強用コードは、液体成分をさらに含んでおり、ゴム補強用コードにおける液体成分の含有率は０．１～２．０質量％の範囲内である。なお、ゴム補強用コードに含まれる液体成分は、例えば、第１の被膜を作製する際に用いられる水性処理剤（第１の被膜用水性処理剤）に含まれる溶媒や、フィラメント自体が持つ水分などの残存などによって構成される。 [Rubber reinforcement cord]
The rubber reinforcing cord of the present embodiment is a cord for reinforcing a rubber product. The rubber reinforcing cord includes at least one strand. The strand includes at least one filament bundle and a first coating provided so as to cover at least a part of the surface of the filament bundle. The filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments. The first coating contains a rubber component and a crosslinking agent. The rubber reinforcing cord of this embodiment further includes a liquid component, and the content of the liquid component in the rubber reinforcing cord is in the range of 0.1 to 2.0% by mass. The liquid component contained in the rubber reinforcing cord is, for example, a solvent contained in an aqueous treatment agent (first aqueous treatment agent for coating) used for producing the first coating, or moisture contained in the filament itself. It is constituted by the remaining etc.
　以下、本実施形態の補強用コードの製造方法について、より詳しく説明する。 Hereinafter, the manufacturing method of the reinforcing cord of this embodiment will be described in more detail.
　本実施形態のゴム補強用コードにおいて、ストランドを構成するフィラメント束は、複数のフィラメントを含む。上記のとおり、フィラメント束は、実質的にポリパラフェニレンテレフタルアミド繊維フィラメントからなる。ここで、「フィラメント束が実質的にポリパラフェニレンテレフタルアミド繊維フィラメントからなる」とは、発明の効果に大きな影響を与えない程度に、フィラメント束が、ポリパラフェニレンテレフタルアミド繊維フィラメント以外のフィラメントを含んでもよいことを意味する。例えば、フィラメント束は、ポリパラフェニレンテレフタルアミド繊維フィラメント以外のフィラメントを、フィラメント束の断面積に占める割合が１０％以下（例えば５％以下や１％以下）の割合で含んでもよい。ポリパラフェニレンテレフタルアミド繊維としては、例えば、帝人株式会社製「トワロン」及び東レ・デュポン株式会社製「ケブラー」が挙げられる。ポリパラフェニレンテレフタルアミド繊維フィラメント以外のフィラメントとしては、ゴム補強用コードの補強用の繊維として一般的に用いられている繊維のフィラメントを用いることができる。フィラメント束は、ポリパラフェニレンテレフタルアミド繊維のみからなっていてもよい。 In the rubber reinforcing cord of the present embodiment, the filament bundle constituting the strand includes a plurality of filaments. As described above, the filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments. Here, “the filament bundle is substantially composed of polyparaphenylene terephthalamide fiber filament” means that the filament bundle includes filaments other than the polyparaphenylene terephthalamide fiber filament to such an extent that the effect of the invention is not greatly affected. It means that it may be included. For example, the filament bundle may include filaments other than polyparaphenylene terephthalamide fiber filaments at a ratio of 10% or less (for example, 5% or less or 1% or less) in the cross-sectional area of the filament bundle. Examples of the polyparaphenylene terephthalamide fiber include “Twaron” manufactured by Teijin Limited and “Kevlar” manufactured by Toray DuPont Co., Ltd. As the filament other than the polyparaphenylene terephthalamide fiber filament, a filament of a fiber generally used as a reinforcing fiber of a rubber reinforcing cord can be used. The filament bundle may consist only of polyparaphenylene terephthalamide fibers.
　フィラメント束に含まれるフィラメントの数は、特に制限はない。フィラメント束は、例えば２００本～２０００本の範囲のフィラメントを含むことができる。 The number of filaments contained in the filament bundle is not particularly limited. The filament bundle can include, for example, a range of 200 to 2000 filaments.
　フィラメント束に含まれるポリパラフェニレンテレフタルアミド繊維フィラメントの表面は、接着強度を高めるための前処理が行われていることが好ましい。前処理剤の好ましい一例は、エポキシ基及びアミノ基からなる群より選ばれる少なくともいずれか１つの官能基を含有する化合物である。前処理剤の例には、アミノシラン、エポキシシラン、ノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、臭素化エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、グリシジルアミン型エポキシ樹脂などが含まれる。具体的な例としては、ナガセケムテックス社のデナコールシリーズ、ＤＩＣ社のエピクロンシリーズ、三菱化学社のエピコートシリーズなどが挙げられる。また、前処理剤として、ポリウレタン樹脂及びイソシアネート化合物も同様に使用できる。例えば、前処理剤として、エポキシ樹脂、ウレタン樹脂及びイソシアネート化合物からなる群より選択される少なくともいずれか１つを含む処理剤を用いてもよい。このような処理剤を用いて前処理することにより、フィラメント束と第１の被膜との間に、エポキシ樹脂、ウレタン樹脂及びイソシアネート化合物からなる群より選択される少なくともいずれか１つを含む樹脂層がさらに設けられる。表面が前処理されたポリパラフェニレンテレフタルアミド繊維フィラメントを用いることによって、マトリックスゴムとゴム補強用コードとの接着性を高めることが可能である。 It is preferable that the surface of the polyparaphenylene terephthalamide fiber filament contained in the filament bundle is subjected to pretreatment for increasing the adhesive strength. A preferred example of the pretreatment agent is a compound containing at least one functional group selected from the group consisting of an epoxy group and an amino group. Examples of the pretreatment agent include aminosilane, epoxysilane, novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin, bisphenol AD type epoxy resin, glycidylamine type epoxy resin, and the like. . Specific examples include Nagase ChemteX's Denacol series, DIC's Epicron series, and Mitsubishi Chemical's Epicoat series. Moreover, a polyurethane resin and an isocyanate compound can be similarly used as a pretreatment agent. For example, as the pretreatment agent, a treatment agent containing at least one selected from the group consisting of an epoxy resin, a urethane resin, and an isocyanate compound may be used. A resin layer containing at least one selected from the group consisting of an epoxy resin, a urethane resin, and an isocyanate compound between the filament bundle and the first film by pretreatment using such a treatment agent. Is further provided. By using a polyparaphenylene terephthalamide fiber filament whose surface is pretreated, it is possible to enhance the adhesion between the matrix rubber and the rubber reinforcing cord.
　ゴム補強用コードに含まれるフィラメント束の数に限定はなく、１本であってもよいし、複数本であってもよい。フィラメント束は、フィラメント束を複数本束ねたものであってもよい。この場合、複数本のフィラメント束のそれぞれは、撚られていてもよいし、撚られていなくてもよい。また、複数本のフィラメント束が合わせられた状態で撚られていてもよいし、撚られていなくてもよい。 The number of filament bundles included in the rubber reinforcing cord is not limited, and may be one or plural. The filament bundle may be a bundle of a plurality of filament bundles. In this case, each of the plurality of filament bundles may be twisted or may not be twisted. Moreover, it may be twisted in a state where a plurality of filament bundles are combined, or may not be twisted.
　第１の被膜は、フィラメント束の少なくとも表面の一部を覆うように設けられている。なお、第１の被膜は、フィラメント束の表面上に直接設けられていてもよいし、他の層（例えば、上述のフィラメントの前処理によって形成された被膜（例えば、上記樹脂層））を介してフィラメント束の表面を覆っていてもよい。 The first coating is provided so as to cover at least a part of the surface of the filament bundle. The first coating may be provided directly on the surface of the filament bundle, or through another layer (for example, a coating (for example, the resin layer) formed by the above-described filament pretreatment). The surface of the filament bundle may be covered.
　第１の被膜は、フィラメント束の表面の少なくとも一部に、後述の第１の被膜用水性処理剤を供給し、それを熱処理によって乾燥させることによって形成される。フィラメント束の表面への第１の水性処理剤の供給は、例えば、フィラメント束を第１の被膜用水性処理剤に含浸させる、又は、フィラメント束の表面の少なくとも一部に第１の被膜用水性処理剤を塗布することによって実施され得る。なお、この際の熱処理により、フィラメント自体が持つ水分及び水性処理剤の溶媒（例えば水）がほぼ除去される。 The first coating is formed by supplying a first aqueous coating agent for coating described later to at least a part of the surface of the filament bundle and drying it by heat treatment. The supply of the first aqueous treatment agent to the surface of the filament bundle may be performed by, for example, impregnating the filament bundle with the first aqueous treatment agent for coating, or at least part of the surface of the filament bundle with the first aqueous coating solution. It can be carried out by applying a treatment agent. In addition, the water | moisture content which the filament itself has, and the solvent (for example, water) of an aqueous processing agent are substantially removed by the heat processing in this case.
　第１の被膜は、ゴム成分を含む。ゴム成分は、ニトリルゴム、水素化ニトリルゴム、カルボキシル変性ニトリルゴム及びカルボキシル変性水素化ニトリルゴムからなる群より選ばれる少なくともいずれか１つを含むことが好ましい。第１の被膜は、ゴム成分として上記ゴムを１種類のみ含んでもよいし、複数種含んでもよい。これらのゴムは、油による膨潤が小さく耐油性に優れる点で好ましい。なお、本明細書において、「ニトリルゴム」という用語は、特に記載がない限り、水素化もカルボキシル変性もされていないニトリルゴム（アクリロニトリル－ブタジエン共重合体ゴム）を意味する。水素化ニトリルゴムのヨウ素価は、通常、１２０以下であり、たとえば、１００以下であってもよい。一例の水素化ニトリルゴムのヨウ素価は、０～５０の範囲にある。 The first coating contains a rubber component. The rubber component preferably contains at least one selected from the group consisting of nitrile rubber, hydrogenated nitrile rubber, carboxyl-modified nitrile rubber, and carboxyl-modified hydrogenated nitrile rubber. The first coating may contain only one type of rubber as a rubber component, or may contain a plurality of types. These rubbers are preferable in that they are less swelled by oil and excellent in oil resistance. In the present specification, the term “nitrile rubber” means a nitrile rubber (acrylonitrile-butadiene copolymer rubber) that is not hydrogenated or carboxyl-modified unless otherwise specified. The iodine value of the hydrogenated nitrile rubber is usually 120 or less, and may be 100 or less, for example. An example hydrogenated nitrile rubber has an iodine value in the range of 0-50.
　第１の被膜は、上記ゴム以外に、他のゴムを含んでいてもよい。他のゴムとしては、ブタジエン・スチレン共重合体、ジカルボキシル化ブタジエン・スチレン共重合体、ビニルピリジン・ブタジエン・スチレン共重合体、クロロプレンゴム、ブタジエンゴム及びクロロスルホン化ポリエチレンなどが挙げられる。 The first film may contain other rubber in addition to the rubber. Examples of other rubbers include butadiene / styrene copolymers, dicarboxylated butadiene / styrene copolymers, vinylpyridine / butadiene / styrene copolymers, chloroprene rubber, butadiene rubber, and chlorosulfonated polyethylene.
　第１の被膜は、さらに架橋剤を含む。第１の被膜が架橋剤を含むことにより、本実施形態のゴム補強用コードは、マトリックスゴムとの接着性を向上できる。架橋剤の例には、Ｐ－キノンジオキシムなどのキノンジオキシム系架橋剤、ラウリルメタアクリレートやメチルメタアクリレートなどのメタアクリレート系架橋剤、ＤＡＦ（ジアリルフマレート）、ＤＡＰ（ジアリルフタレート）、ＴＡＣ（トリアリルシアヌレート）及びＴＡＩＣ（トリアリルイソシアヌレート）などのアリル系架橋剤、ビスマレイミド、フェニルマレイミド及びＮ，Ｎ’－ｍ－フェニレンジマレイミドなどのマレイミド系架橋剤、芳香族又は脂肪族の有機ジイソシアネート、ポリイソシアネート、ブロックドイソシアネート、ブロックドポリイシシアネート、芳香族ニトロソ化合物、硫黄、及び過酸化物が含まれる。これらの架橋剤は、単独で用いてもよいし、複数種を組み合わせて用いてもよい。これらの架橋剤は、第１の被膜に含まれるゴムの種類、及びゴム補強用コードが埋め込まれるマトリックスゴムの種類などを考慮して選択される。なお、これら架橋剤は、水分散体の形態で用いられることが、第１の被膜を作製するための水性処理剤中に架橋剤を均質に存在させるためには好ましい。架橋剤は、マレイミド系架橋剤、有機ジイソシアネート、及び芳香族ニトロソ化合物からなる群より選ばれる少なくとも１つであってもよい。 The first film further contains a cross-linking agent. When the first coating contains a cross-linking agent, the rubber reinforcing cord of the present embodiment can improve the adhesion with the matrix rubber. Examples of crosslinking agents include quinonedioxime crosslinking agents such as P-quinonedioxime, methacrylate crosslinking agents such as lauryl methacrylate and methyl methacrylate, DAF (diallyl fumarate), DAP (diallyl phthalate), TAC (Triallyl cyanurate) and TAIC (triallyl isocyanurate) and other allyl crosslinking agents, bismaleimide, phenylmaleimide and maleimide crosslinking agents such as N, N'-m-phenylenedimaleimide, aromatic or aliphatic Organic diisocyanates, polyisocyanates, blocked isocyanates, blocked polyisocyanates, aromatic nitroso compounds, sulfur, and peroxides are included. These crosslinking agents may be used alone or in combination of two or more. These crosslinking agents are selected in consideration of the type of rubber contained in the first coating, the type of matrix rubber in which the rubber reinforcing cord is embedded, and the like. In addition, it is preferable that these crosslinking agents are used in the form of an aqueous dispersion so that the crosslinking agent is present uniformly in the aqueous treatment agent for producing the first coating film. The crosslinking agent may be at least one selected from the group consisting of a maleimide crosslinking agent, an organic diisocyanate, and an aromatic nitroso compound.
　上記の架橋剤の中でも、マレイミド系架橋剤及びポリイソシアネートからなる群より選ばれる少なくとも１つを用いることが好ましい。マレイミド系架橋剤の中でも、４，４’－ビスマレイミドジフェニルメタンは、水に分散したときの安定性がよく、架橋効果が高く、架橋後の耐熱性も高いので、好適に用いられる。マレイミド系架橋剤及びポリイソシアネートは、それぞれ、ゴムラテックスと組み合わせることによって、補強用コードとマトリックスゴムとの接着性を特異的に高めることができる。特に、カルボキシル変性された水素化ニトリルゴムのラテックスとマレイミド系架橋剤との組み合わせは、接着性をより高めることができるため好ましい。 Among the above crosslinking agents, it is preferable to use at least one selected from the group consisting of maleimide crosslinking agents and polyisocyanates. Among the maleimide crosslinking agents, 4,4'-bismaleimide diphenylmethane is preferably used because it has good stability when dispersed in water, has a high crosslinking effect, and has high heat resistance after crosslinking. The maleimide-based crosslinking agent and polyisocyanate can specifically enhance the adhesion between the reinforcing cord and the matrix rubber by combining with the rubber latex. In particular, a combination of a latex of a carboxyl-modified hydrogenated nitrile rubber and a maleimide-based crosslinking agent is preferable because the adhesion can be further improved.
　第１の被膜は、さらに充填材を含んでいてもよい。充填材の例には、カーボンブラックやシリカなどの共有結合系化合物の微粒子、難溶性塩の微粒子、金属酸化物の微粒子、金属水酸化物の微粒子、タルクなどの複合金属酸化物塩の微粒子が含まれる。これらの中でも、カーボンブラック及びシリカからなる群より選ばれる少なくとも１つが好ましい。 The first film may further contain a filler. Examples of fillers include fine particles of covalently bonded compounds such as carbon black and silica, fine particles of hardly soluble salts, fine particles of metal oxide, fine particles of metal hydroxide, fine particles of complex metal oxide salts such as talc. included. Among these, at least one selected from the group consisting of carbon black and silica is preferable.
　カーボンブラックの平均粒径は、５～３００ｎｍの範囲にあることが好ましく、例えば１００～２００ｎｍの範囲あり、より好ましくは１３０～１７０ｎｍの範囲にある。シリカの平均粒径は、５～２００ｎｍの範囲にあることが好ましく、例えば７～１００ｎｍの範囲にあり、より好ましくは７～３０ｎｍの範囲にある。ここで平均粒径とは、５０個以上の粒子について透過型電子顕微鏡を用いて粒径を測定し、その粒径の合計を測定粒子数で割った値のことである。なお粒子が球形ではない場合には、各粒子の最も長い径と最も短い径の平均を粒径とした。 The average particle size of carbon black is preferably in the range of 5 to 300 nm, for example, in the range of 100 to 200 nm, and more preferably in the range of 130 to 170 nm. The average particle diameter of silica is preferably in the range of 5 to 200 nm, for example in the range of 7 to 100 nm, and more preferably in the range of 7 to 30 nm. Here, the average particle diameter is a value obtained by measuring the particle diameter of 50 or more particles using a transmission electron microscope and dividing the total of the particle diameters by the number of measured particles. When the particles were not spherical, the average of the longest diameter and the shortest diameter of each particle was taken as the particle size.
　充填材は、ゴム中に分散して存在することで、被膜の引張強度や引裂き強度などの特性を向上させる効果を有する。これらの効果に加え、充填材は、繊維と被膜との間、及び、被膜とマトリックスゴムとの間において、接着成分の凝集力を高めることによって接着強度を向上させる効果もある。なお、これらの効果には、充填材の粒径と配合量とが大きく影響する。 The filler has an effect of improving the properties such as the tensile strength and tear strength of the coating by being dispersed in the rubber. In addition to these effects, the filler also has the effect of improving the adhesive strength by increasing the cohesive strength of the adhesive component between the fiber and the coating and between the coating and the matrix rubber. These effects are greatly influenced by the particle size and blending amount of the filler.
　第１の被膜は、レゾルシン－ホルムアルデヒド縮合物を含まないことが好ましい。その場合、第１の被膜を作製する際に、ホルムアルデヒド及びアンモニアなどの環境負荷の大きい物質を使用しなくてもよくなるため、作業者のための環境対策が不要になる。ただし、第１の被膜は、レゾルシン－ホルムアルデヒド縮合物を含んでいてもよい。 The first coating preferably contains no resorcin-formaldehyde condensate. In that case, when producing the first coating, it is not necessary to use a substance with a large environmental load such as formaldehyde and ammonia, so that no environmental measures are required for the operator. However, the first film may contain a resorcin-formaldehyde condensate.
　第１の被膜は、ゴム成分及び架橋剤に加えて、充填材や、さらに他の成分（例えば、上記充填材として添加される金属酸化物以外の金属酸化物や、樹脂など）をさらに含んでいてもよい。 In addition to the rubber component and the crosslinking agent, the first coating film further includes a filler and further other components (for example, a metal oxide other than the metal oxide added as the filler or a resin). May be.
　第１の被膜におけるゴム成分及び架橋剤の含有率は、特には限定されない。第１の被膜におけるゴム成分の含有率は、例えば５０～９０質量％とできる。また、第１の被膜における架橋剤の含有率は、例えば１０～５０質量％の範囲内とできる。 The contents of the rubber component and the crosslinking agent in the first coating are not particularly limited. The content of the rubber component in the first coating can be set to 50 to 90% by mass, for example. In addition, the content of the crosslinking agent in the first coating can be in the range of 10 to 50% by mass, for example.
　フィラメント束の少なくとも表面に設けられる第１の被膜の質量は、特には限定されず適宜調整すればよいが、フィラメント束の質量の５～３５％の範囲内となるように設けられることが好ましい。第１の被膜の質量は、フィラメント束の質量の１０～２５％の範囲であってもよいし、１２～２０質量％の範囲内であってもよい。第１の被膜の質量が多すぎる場合、ゴム製品内におけるゴム補強用コードの寸法安定性の低下や、ゴム補強用コードの弾性率の低下などの不具合が発生することがある。一方、第１の被膜の質量が少なすぎる場合、ストランドがほつれやすくなったり、第１の被膜により繊維を保護する機能が低下したりして、その結果、ゴム製品の寿命が低下する場合がある。 The mass of the first coating film provided on at least the surface of the filament bundle is not particularly limited and may be adjusted as appropriate, but it is preferably provided so as to be in the range of 5 to 35% of the mass of the filament bundle. The mass of the first coating may be in the range of 10 to 25% of the mass of the filament bundle, or may be in the range of 12 to 20% by mass. When the mass of the first coating is too large, problems such as a decrease in the dimensional stability of the rubber reinforcing cord in the rubber product and a decrease in the elastic modulus of the rubber reinforcing cord may occur. On the other hand, when the mass of the first coating is too small, the strands are likely to fray or the function of protecting the fibers by the first coating is reduced, and as a result, the life of the rubber product may be reduced. .
　マトリックスゴムとの接着性を向上させるために、本実施形態のゴム補強用コードは、第１の被膜上に形成された第２の被膜をさらに備えてもよい。第２の被膜を形成する処理剤は、第１の被膜用水性処理剤と同じでもよいし、異なってもよい。たとえば、成分や溶媒が第１の被膜用水性処理剤とは異なる処理剤で第２の被膜を形成してもよい。マトリックスゴムとの接着性をさらに向上させるために、第２の被膜上にさらなる被膜を設けることも可能である。 In order to improve the adhesion with the matrix rubber, the rubber reinforcing cord of the present embodiment may further include a second coating formed on the first coating. The treatment agent for forming the second coating may be the same as or different from the first aqueous treatment agent for coating. For example, you may form a 2nd film with a processing agent in which a component and a solvent differ from the aqueous processing agent for 1st films. In order to further improve the adhesion to the matrix rubber, it is possible to provide a further coating on the second coating.
　本実施形態のゴム補強用コードの撚り数は、特には限定されない。１本のストランドに加えられる撚り（以下、下撚りということもある）の数は、例えば２０～１６０回／ｍの範囲、３０～１２０回／ｍの範囲、又は、４０～１００回／ｍの範囲であってよい。さらに、複数のストランドに加えられた撚り（以下、上撚りということもある）の数も同様に、例えば２０～１６０回／ｍの範囲、３０～１２０回／ｍの範囲、又は、４０～１００回／ｍの範囲であってよい。下撚り方向と上撚り方向が同じラング撚りであってもよく、下撚り方向と上撚り方向が逆方向のモロ撚りでもよい。撚りの方向に限定はなく、Ｓ方向であってもよいし、Ｚ方向であってもよい。 The number of twists of the rubber reinforcing cord of the present embodiment is not particularly limited. The number of twists (hereinafter sometimes referred to as the lower twist) applied to one strand is, for example, in the range of 20 to 160 times / m, in the range of 30 to 120 times / m, or in the range of 40 to 100 times / m. It may be a range. Furthermore, the number of twists (hereinafter sometimes referred to as upper twists) applied to the plurality of strands is also in the range of, for example, 20 to 160 times / m, 30 to 120 times / m, or 40 to 100. It may be in the range of times / m. The Lang twist may be the same as the lower twist direction and the upper twist direction, and the Moro twist may be the reverse of the lower twist direction and the upper twist direction. There is no limitation in the direction of twist, and it may be the S direction or the Z direction.
　本実施形態のゴム補強用コードにおける液体成分の含有率は、０．１～２．０質量％の範囲内である。なお、上述したように、この液体成分とは、被膜を作製する際に用いられる水性処理剤に含まれる溶媒（例えば水）や、フィラメント自体が持つ水分などの残存である。本実施形態のゴム補強用コードでは、第１の被膜を作製する際の熱処理において、さらには、本実施形態のゴム補強用コードが第２の被膜をさらに含む場合は第２の被膜を作製する際の熱処理において、０．１～２．０質量％の範囲内でゴム補強用コード中に液体成分が残存するように熱量を調整して熱処理を行うことにより、ポリパラフェニレンテレフタルアミド繊維の引張強度の低下を抑制又は低下の度合を小さく抑えつつ、ゴムマトリックスとの十分な接着強度が実現できる。液体成分の含有率が０．１質量％未満、すなわち第１の被膜作製時の熱処理、さらには第２の被膜作製時の熱処理が、被膜作製のための処理剤の溶媒、及び、繊維に含まれる水分がほぼ全てなくなるように実施された場合は、ポリパラフェニレンテレフタルアミド繊維の引張強度が低下してしまい、その結果ゴム補強用コードの引張強度が低下する。一方、液体成分の含有率が２．０質量％を超える場合は、マトリックスゴムとの十分な接着強度を実現できる程度に十分な熱量が被膜に加えられなかったことになるので、マトリックスゴムとの十分な接着強度を実現できるゴム補強用コードを得ることができない。 The content of the liquid component in the rubber reinforcing cord of the present embodiment is in the range of 0.1 to 2.0% by mass. As described above, this liquid component is a residual solvent such as a solvent (for example, water) contained in an aqueous treatment agent used when a film is formed or moisture contained in the filament itself. In the rubber reinforcing cord of the present embodiment, in the heat treatment when the first coating is produced, the second coating is produced when the rubber reinforcing cord of the present embodiment further includes the second coating. In the heat treatment, the polyparaphenylene terephthalamide fiber is pulled by adjusting the amount of heat so that the liquid component remains in the rubber reinforcing cord within the range of 0.1 to 2.0% by mass. Sufficient adhesive strength with the rubber matrix can be realized while suppressing the decrease in strength or suppressing the degree of decrease. The content of the liquid component is less than 0.1% by mass, that is, the heat treatment at the time of producing the first film, and further the heat treatment at the time of producing the second film are contained in the solvent of the treatment agent for producing the film and the fiber When it is carried out so that almost all the water is removed, the tensile strength of the polyparaphenylene terephthalamide fiber is lowered, and as a result, the tensile strength of the rubber reinforcing cord is lowered. On the other hand, when the content of the liquid component exceeds 2.0% by mass, a sufficient amount of heat has not been applied to the coating so that sufficient adhesive strength with the matrix rubber can be realized. It is not possible to obtain a rubber reinforcing cord capable of realizing sufficient adhesive strength.
　より高い引張強度と、より高い接着強度とを有するゴム補強用コードを得るために、ゴム補強用コードにおける液体成分の含有率は、０．２～１．５質量％であることが好ましく、０．３～１．３質量％であることがより好ましい。 In order to obtain a rubber reinforcing cord having higher tensile strength and higher adhesive strength, the content of the liquid component in the rubber reinforcing cord is preferably 0.2 to 1.5% by mass, More preferably, the content is 3 to 1.3% by mass.
　ここで、本発明において特定される「ゴム補強用コードにおける液体成分の含有率」とは、次のように求められる値のことである。ゴム補強用コードから長さ５ｍのコードを試料として採取し、その試料を電子天秤で計測し、この値をコードの質量Ａとする。その試料を１５０℃に加温した乾燥機に３０分間入れて試料中の溶媒を除去し、デシケーターに３０分入れた後に電子天秤で計測した値を質量Ｂとし、質量Ａと質量Ｂとの差をコードに含まれる液体成分の質量（Ａ－Ｂ）とした。コードの質量Ａに対する、コードに含まれる液体成分の質量（Ａ－Ｂ）の百分率（{（Ａ－Ｂ）／Ａ｝×１００）を液体成分の含有率（％）とする。なお、ここでは、処理剤の溶媒が水であることを想定して、試料から水を完全に除去するために１５０℃、３０分間の熱処理を実施しているが、水以外の溶媒を用いている場合は、その溶媒を完全に除去できるように適切な加熱温度及び加熱時間を設定すればよい。 Here, the “content ratio of the liquid component in the rubber reinforcing cord” specified in the present invention is a value obtained as follows. A 5 m long cord is taken as a sample from the rubber reinforcing cord, the sample is measured with an electronic balance, and this value is taken as the mass A of the cord. The sample was placed in a dryer heated to 150 ° C. for 30 minutes to remove the solvent in the sample. Was the mass (AB) of the liquid component contained in the cord. The percentage ({(AB) / A} × 100) of the mass (AB) of the liquid component contained in the cord with respect to the mass A of the cord is defined as the liquid component content (%). Here, assuming that the solvent of the treatment agent is water, heat treatment is performed at 150 ° C. for 30 minutes in order to completely remove water from the sample, but a solvent other than water is used. If it is, an appropriate heating temperature and heating time may be set so that the solvent can be completely removed.
　ゴム補強用コードが、第１の被膜上に設けられた第２の被膜をさらに含んでいる場合は、第２の被膜を作製する際にも熱処理が行われることになる。したがって、第２の被膜を作製する際の熱処理も、引張強度及び接着強度の低下を防ぐような範囲内で実施されることが好ましく、その場合、ゴム補強用コードにおける液体成分に第２の被膜に残存する溶媒などの液体が含まれる場合もある。したがって、第２の被膜を含むゴム補強用コードの場合は、ゴム補強用コードにおける液体成分の含有率が、０．５～２．０質量％の範囲内であることが好ましい。 When the rubber reinforcing cord further includes a second coating provided on the first coating, heat treatment is also performed when the second coating is produced. Therefore, it is preferable that the heat treatment for producing the second coating is also performed within a range that prevents a decrease in tensile strength and adhesive strength. In this case, the second coating is applied to the liquid component in the rubber reinforcing cord. In some cases, a liquid such as a remaining solvent is contained. Therefore, in the case of the rubber reinforcing cord including the second coating, it is preferable that the content of the liquid component in the rubber reinforcing cord is in the range of 0.5 to 2.0% by mass.
［ゴム補強用コードの製造方法］
　本実施形態のゴム補強用コードの製造方法の一例を以下に説明する。なお、本実施形態のゴム補強用コードについて説明した事項は以下の製造方法に適用できるため、重複する説明を省略する場合がある。また、以下の製造方法で説明した事項は、本実施形態のゴム補強用コードに適用できる。この製造方法の一例は、以下の工程を含む。 [Method of manufacturing rubber reinforcing cord]
An example of a method for manufacturing the rubber reinforcing cord of this embodiment will be described below. In addition, since the matter demonstrated about the rubber | gum reinforcement cord of this embodiment is applicable to the following manufacturing methods, the overlapping description may be abbreviate | omitted. The matters described in the following manufacturing method can be applied to the rubber reinforcing cord of the present embodiment. An example of this manufacturing method includes the following steps.
　まず、複数のフィラメントを束ねてフィラメント束を作製し、さらに第１の被膜の作製に用いられる水性処理剤（第１の被膜用水性処理剤）を準備する。次に、フィラメント束の表面の少なくとも一部に第１の被膜用水性処理剤を供給する。その後、第１の被膜用水性処理剤中の溶媒を除去するための熱処理を行う。具体例として、まず１０００本のフィラメントを引き揃えて１つの束とし、その束の表面に第１の被膜用水性処理剤を塗布又は含浸させる。その後、第１の被膜用水性処理剤中の溶媒を熱処理によって除去する。フィラメント束は、実質的にポリパラフェニレンテレフタルアミド繊維フィラメントからなる。 First, a plurality of filaments are bundled to produce a filament bundle, and further an aqueous treatment agent (first aqueous treatment agent for coating) used for producing the first coating is prepared. Next, the first aqueous coating agent for coating is supplied to at least a part of the surface of the filament bundle. Thereafter, heat treatment is performed to remove the solvent in the first aqueous coating agent. As a specific example, first, 1000 filaments are aligned to form one bundle, and the surface of the bundle is coated or impregnated with the first aqueous coating agent for coating. Thereafter, the solvent in the first aqueous coating agent for coating is removed by heat treatment. The filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments.
　上記工程によって、フィラメント束の表面の少なくとも一部に第１の被膜が形成される。第１の被膜用水性処理剤をフィラメント束の表面の少なくとも一部に供給する方法に限定はなく、たとえば、フィラメント束の表面に第１の被膜用水性処理剤を塗布してもよいし、フィラメント束を第１の被膜用水性処理剤中に浸漬してもよい。 The first film is formed on at least a part of the surface of the filament bundle by the above process. The method for supplying the first aqueous coating agent for coating to at least a part of the surface of the filament bundle is not limited. For example, the first aqueous coating agent for coating may be applied to the surface of the filament bundle. The bundle may be immersed in the first aqueous coating agent for coating.
　第１の被膜用水性処理剤の溶媒を除去するための熱処理の条件は、特に限定されないが、熱処理後に得られるコードの液体成分の含有率が０．１～２．０質量％となるように、処理温度及び処理時間を適宜調整する。好ましくは、熱処理後に得られるコードの液体成分の含有率が０．２～１．５質量％、より好ましくは０．３～１．３質量％となるように、処理温度及び処理時間を適宜調整することである。処理温度は、例えば２２０℃以下が望ましい。処理時間は特に限定されず、熱処理の温度を考慮し、付与される熱量が完成したゴム補強用コードにおける液体成分の含有率が本実施形態で特定する範囲内（０．１～２．０質量％）を実現できるような熱量となるように、適宜調整するとよい。 The conditions of the heat treatment for removing the solvent of the first aqueous coating agent for coating are not particularly limited, but the content of the liquid component of the cord obtained after the heat treatment is 0.1 to 2.0% by mass. The processing temperature and processing time are adjusted appropriately. Preferably, the treatment temperature and treatment time are appropriately adjusted so that the content of the liquid component of the cord obtained after the heat treatment is 0.2 to 1.5% by mass, more preferably 0.3 to 1.3% by mass. It is to be. The processing temperature is preferably 220 ° C. or lower, for example. The treatment time is not particularly limited, and in consideration of the heat treatment temperature, the amount of heat applied is within the range specified in this embodiment by the liquid component content in the completed rubber reinforcing cord (0.1 to 2.0 mass). %) May be adjusted as appropriate so that the amount of heat can be realized.
　第１の被膜が形成されたフィラメント束は、通常、一方向に撚られる。撚る方向は、Ｓ方向であってもよいし、Ｚ方向であってもよい。フィラメント束に含まれるフィラメントの数及びフィラメント束の撚り数は、上述したため、説明を省略する。このようにして、本実施形態のゴム補強用コードを製造できる。なお、第１の被膜が形成されたフィラメントの束を複数形成し、それら複数のフィラメント束を束ねて上撚りを加えてもよい。上撚りの方向は、フィラメント束の撚りの方向（下撚りの方向）と同じであってもよいし、異なってもよい。また、第１の被膜が形成されたフィラメント束を複数形成し、フィラメント束それぞれには撚りを与えず、複数のフィラメント束を束ねたものに撚りを加えてもよい。 The filament bundle on which the first film is formed is usually twisted in one direction. The twisting direction may be the S direction or the Z direction. Since the number of filaments contained in the filament bundle and the number of twists of the filament bundle have been described above, description thereof will be omitted. In this way, the rubber reinforcing cord of this embodiment can be manufactured. Note that a plurality of bundles of filaments on which the first film is formed may be formed, and the plurality of bundles of filaments may be bundled to add an upper twist. The direction of the upper twist may be the same as or different from the direction of twist of the filament bundle (the direction of the lower twist). Alternatively, a plurality of filament bundles on which the first film is formed may be formed, and a twist may be added to a bundle of a plurality of filament bundles without giving a twist to each filament bundle.
　なお、フィラメント束に撚りを加えてから第１の被膜を形成してもよい。フィラメントの種類、数、及び撚り数は、上述した通りである。 The first film may be formed after twisting the filament bundle. The type, number, and number of twists of the filament are as described above.
　本実施形態の製造方法の好ましい一例では、フィラメント束に第１の被膜用水性処理剤を塗布又は含浸した後、その束ねたものを一方向に撚ることによって、ゴム補強用コードを形成する。 In a preferred example of the manufacturing method of the present embodiment, the first bundle of aqueous coating agent is applied or impregnated into the filament bundle, and then the bundle is twisted in one direction to form a rubber reinforcing cord.
　第１の被膜の上に第２の被膜を形成する場合には、第１の被膜の上に第２の被膜を形成するための処理剤を塗布し、その処理剤中の溶媒を除去することによって第２の被膜を形成すればよい。この第２の被膜の種類は、ゴム補強用コードが適用されるゴム製品のマトリックスゴムに合わせて適宜選択することができ、特に接着性向上の観点から選択されることが望ましい。 When the second film is formed on the first film, a treatment agent for forming the second film is applied on the first film, and the solvent in the treatment agent is removed. The second film may be formed by The type of the second coating can be appropriately selected according to the matrix rubber of the rubber product to which the rubber reinforcing cord is applied, and is particularly preferably selected from the viewpoint of improving adhesiveness.
　第２の被膜用処理剤の溶媒を除去するための熱処理の条件は、特に限定されないが、熱処理後に得られるコードの液体成分の含有率が０．５～２．０質量％となるように、処理温度及び処理時間を適宜調整することが好ましい。 The conditions of the heat treatment for removing the solvent of the second coating treatment agent are not particularly limited, but the content of the liquid component of the cord obtained after the heat treatment is 0.5 to 2.0% by mass. It is preferable to appropriately adjust the treatment temperature and the treatment time.
　次に、第１の被膜用水性処理剤について説明する。 Next, the first aqueous treatment agent for coating will be described.
　第１の被膜用水性処理剤は、ニトリルゴム、水素化ニトリルゴム、カルボキシル変性されたニトリルゴム、及びカルボキシル変性された水素化ニトリルゴムからなる群より選ばれる少なくとも１つのゴムのラテックスを含むことが好ましい。水性処理剤は、これらのゴムラテックスの１種類のみを含んでもよいし、これらのゴムラテックスの複数種を含んでもよい。 The first aqueous coating agent for coating may include a latex of at least one rubber selected from the group consisting of nitrile rubber, hydrogenated nitrile rubber, carboxyl-modified nitrile rubber, and carboxyl-modified hydrogenated nitrile rubber. preferable. The aqueous treatment agent may contain only one of these rubber latexes, or may contain a plurality of these rubber latexes.
　第１の被膜用水性処理剤は、上記のゴムラテックス以外に、他のゴムラテックスを含んでもよい。他のゴムラテックスの例には、ブタジエン・スチレン共重合体ラテックス、ジカルボキシル化ブタジエン・スチレン共重合体ラテックス、ビニルピリジン・ブタジエン・スチレンターポリマーラテックス、クロロプレンラテックス、ブタジエンラテックス、クロロスルホン化ポリエチレンラテックスが含まれる。水性処理剤は、これらのゴムラテックスを複数種含んでもよい。 The first aqueous coating agent for coating may contain other rubber latex in addition to the above rubber latex. Other rubber latex examples include butadiene / styrene copolymer latex, dicarboxylated butadiene / styrene copolymer latex, vinylpyridine / butadiene / styrene terpolymer latex, chloroprene latex, butadiene latex, and chlorosulfonated polyethylene latex. included. The aqueous treatment agent may contain a plurality of these rubber latexes.
　第１の被膜用水性処理剤は、さらに架橋剤を含む。第１の被膜用水性処理剤に含まれる架橋剤は、第１の被膜に含まれる架橋剤として上記に説明したものと同じであるため、ここでは説明を省略する。なお、架橋剤は、水分散体の形態で用いることが、水性処理剤中に均質に存在させるためには好ましい。 The first aqueous coating agent for coating further contains a crosslinking agent. Since the crosslinking agent contained in the first aqueous coating agent for coating is the same as that described above as the crosslinking agent contained in the first coating, description thereof is omitted here. In addition, it is preferable to use a crosslinking agent in the form of an aqueous dispersion in order to make it exist uniformly in an aqueous processing agent.
　第１の被膜用水性処理剤は、さらに充填材を含んでいてもよい。第１の被膜用水性処理剤に含まれる充填材は、第１の被膜に含まれる充填材として上記に説明したものと同じであるため、ここでは説明を省略する。 The first aqueous coating agent for coating may further contain a filler. Since the filler contained in the first aqueous coating agent for coating is the same as that described above as the filler contained in the first coating, description thereof is omitted here.
　第１の被膜用水性処理剤は、レゾルシン－ホルムアルデヒド縮合物を含まないことが好ましい。ただし、第１の被膜用水性処理剤は、レゾルシン－ホルムアルデヒド縮合物を含んでもよい。 It is preferable that the first aqueous treatment agent for coating does not contain a resorcin-formaldehyde condensate. However, the first aqueous coating agent for coating may contain a resorcin-formaldehyde condensate.
　第１の被膜用水性処理剤は、ゴムラテックス及び架橋剤に加えて、充填材や、さらに他の成分を含んでもよい。たとえば、第１の被膜用水性処理剤は、樹脂、可塑剤、老化防止剤、安定剤、上記充填材として添加される金属酸化物以外の金属酸化物などを含んでいてもよい。ただし、水性処理剤は、樹脂を含まないものであってもよい。 The first aqueous coating agent for coating may contain a filler and further other components in addition to the rubber latex and the crosslinking agent. For example, the first aqueous coating agent for coating may contain a resin, a plasticizer, an anti-aging agent, a stabilizer, a metal oxide other than the metal oxide added as the filler, and the like. However, the aqueous treatment agent may not contain a resin.
［ゴム製品］
　本実施形態のゴム製品は、本実施形態のゴム補強用コードで補強されたゴム製品である。ゴム製品に特に限定はない。本実施形態のゴム製品の例には、自動車や自転車のタイヤ、及び、伝動ベルトなどが含まれる。伝動ベルトの例には、噛み合い伝動ベルトや摩擦伝動ベルトなどが含まれる。噛み合い伝動ベルトの例には、自動車用タイミングベルトなどに代表される歯付きベルトが含まれる。摩擦伝動ベルトの例には、平ベルト、丸ベルト、Ｖベルト、Ｖリブドベルトなどが含まれる。すなわち、本実施形態のゴム製品は、歯付ベルト、平ベルト、丸ベルト、Ｖベルト、又はＶリブドベルトであってもよい。 [Rubber product]
The rubber product of the present embodiment is a rubber product reinforced with the rubber reinforcing cord of the present embodiment. There is no particular limitation on the rubber product. Examples of rubber products of the present embodiment include automobile and bicycle tires, transmission belts, and the like. Examples of the transmission belt include a meshing transmission belt and a friction transmission belt. Examples of the meshing transmission belt include a toothed belt represented by an automobile timing belt and the like. Examples of the friction transmission belt include a flat belt, a round belt, a V belt, a V-ribbed belt, and the like. That is, the rubber product of the present embodiment may be a toothed belt, a flat belt, a round belt, a V belt, or a V-ribbed belt.
　本実施形態のゴム製品は、本実施形態のゴム補強用コードをゴム組成物（マトリックスゴム）に埋め込むことによって形成されている。ゴム補強用コードをマトリックスゴム内に埋め込む方法は特に限定されず、公知の方法を適用してもよい。本実施形態のゴム製品（たとえばゴムベルト）には、本実施形態のゴム補強用コードが埋め込まれている。そのため、本実施形態のゴム製品は、高い耐屈曲疲労性を備えている。したがって、本実施形態のゴム製品は、車輌用エンジンのタイミングベルトや、車輌用の補機駆動用ベルトなどの用途に特に適している。 The rubber product of the present embodiment is formed by embedding the rubber reinforcing cord of the present embodiment in a rubber composition (matrix rubber). The method for embedding the rubber reinforcing cord in the matrix rubber is not particularly limited, and a known method may be applied. The rubber reinforcing cord of this embodiment is embedded in the rubber product (for example, rubber belt) of this embodiment. Therefore, the rubber product of the present embodiment has high bending fatigue resistance. Therefore, the rubber product of the present embodiment is particularly suitable for applications such as a timing belt for a vehicle engine and a belt for driving an auxiliary machine for a vehicle.
　本実施形態のゴム補強用コードが埋め込まれるゴム組成物に含まれるゴムは、特に限定されず、クロロプレンゴム、クロロスルホン化ポリエチレンゴム、エチレンプロピレンゴム、水素化ニトリルゴムなどであってもよい。水素化ニトリルゴムは、アクリル酸亜鉛誘導体（たとえばメタクリル酸亜鉛）を分散させた水素化ニトリルゴムであってもよい。水素化ニトリルゴム及びアクリル酸亜鉛誘導体を分散させた水素化ニトリルゴムから選ばれる少なくとも１つのゴムは、耐水性及び耐油性の観点から、好ましい。マトリックスゴムは、さらに、カルボキシル変性された水素化ニトリルゴムを含んでもよい。なお、ゴム補強用コードの被膜とゴム製品のゴム組成物とが同じ種類のゴムを含むか、又は、同じ種類のゴムからなることが、接着性の点で好ましい。 The rubber contained in the rubber composition in which the rubber reinforcing cord of the present embodiment is embedded is not particularly limited, and may be chloroprene rubber, chlorosulfonated polyethylene rubber, ethylene propylene rubber, hydrogenated nitrile rubber, or the like. The hydrogenated nitrile rubber may be a hydrogenated nitrile rubber in which a zinc acrylate derivative (for example, zinc methacrylate) is dispersed. At least one rubber selected from hydrogenated nitrile rubber and hydrogenated nitrile rubber in which a zinc acrylate derivative is dispersed is preferable from the viewpoint of water resistance and oil resistance. The matrix rubber may further contain a carboxyl-modified hydrogenated nitrile rubber. In addition, it is preferable in terms of adhesiveness that the coating of the rubber reinforcing cord and the rubber composition of the rubber product contain the same type of rubber or be made of the same type of rubber.
　ゴム製品の一例として、歯付きベルトを図１に示す。図１に示す歯付ベルト１は、ベルト本体１１と、複数のゴム補強用コード１２とを含む。ベルト本体１１は、ベルト部１３と、一定間隔でベルト部１３から突き出した複数の歯部１４とを含む。ゴム補強用コード１２は、ベルト部１３の内部に、ベルト部１３の長手方向と平行となるように埋め込まれている。ゴム補強用コード１２は、本実施形態のゴム補強用コードである。 As an example of rubber products, a toothed belt is shown in FIG. The toothed belt 1 shown in FIG. 1 includes a belt main body 11 and a plurality of rubber reinforcing cords 12. The belt body 11 includes a belt portion 13 and a plurality of tooth portions 14 protruding from the belt portion 13 at regular intervals. The rubber reinforcing cord 12 is embedded in the belt portion 13 so as to be parallel to the longitudinal direction of the belt portion 13. The rubber reinforcing cord 12 is the rubber reinforcing cord of the present embodiment.
　以下、実施例及び比較例を挙げて、本発明の実施形態をさらに具体的に説明する。 Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples and comparative examples.
［実施例１～１０及び比較例１～６］
　＜ゴム補強用コードの製造＞
　まず、エポキシ樹脂を含む前処理剤によって前処理が施された東レ・デュポン社製の「ケブラー２９」（１６７０ｄｔｅｘ）を準備した。この「ケブラー２９」を１０００本集束し、これをフィラメント束として用いた。このフィラメント束を以下の表１に示す組成の第１の被膜用水性処理剤に浸漬した後、２００℃の熱処理により溶媒を蒸発させて、表３及び４に示す「液体成分の含有率」となるように第１の被膜を形成した。なお、第１の被膜用水性処理剤の固形分は２０質量％であり、第１の被膜の質量はフィラメント束の質量の２０％であった。なお、「液体成分の含有率」は、熱処理の時間を変えることによって調整した。このように作製された、第１の被膜付きのフィラメント束を４０回／ｍの割合でＺ撚りに下撚りし、それを２本束ねて１００回／ｍの割合でＺ撚りに上撚りして、ゴム補強用コードを得た。得られたゴム補強用コードについて、液体成分の含有率、引張強度及び接着強度を測定した。液体成分の含有率、引張強度及び接着強度の測定方法は、以下のとおりである。 [Examples 1 to 10 and Comparative Examples 1 to 6]
<Manufacture of rubber reinforcing cord>
First, “Kevlar 29” (1670 dtex) manufactured by Toray DuPont, which was pretreated with a pretreatment agent containing an epoxy resin, was prepared. 1000 pieces of the “Kevlar 29” were converged and used as a filament bundle. After immersing this filament bundle in the first aqueous coating agent for coating having the composition shown in Table 1 below, the solvent was evaporated by a heat treatment at 200 ° C., and the “content ratio of liquid component” shown in Tables 3 and 4 was obtained. The 1st film was formed so that it might become. Note that the solid content of the first aqueous coating agent for coating was 20% by mass, and the mass of the first coating was 20% of the mass of the filament bundle. The “liquid component content” was adjusted by changing the heat treatment time. The filament bundle with the first coating produced in this manner is twisted into a Z twist at a rate of 40 turns / m, and two of them are bundled and twisted into a Z twist at a rate of 100 turns / m. A rubber reinforcing cord was obtained. About the obtained rubber | gum reinforcement cord, the content rate, tensile strength, and adhesive strength of a liquid component were measured. The measuring method of the content rate of a liquid component, tensile strength, and adhesive strength is as follows.
　＜液体成分の含有率＞
　フィラメント束を第１の被膜用水性処理剤に浸漬した後に実施された熱処理後３０分以内に、得られたゴム補強用コードから長さ５ｍのコードを試料として採取した。その試料を電子天秤で計測し、この値をコードの質量Ａとした。次にその試料を１５０℃に加温した乾燥機に３０分間入れて試料中の溶媒を除去し、デシケーターに３０分入れた後に電子天秤で計測した値を質量Ｂとした。質量Ａと質量Ｂとの差をコードに含まれる液体成分の質量（Ａ－Ｂ）とした。コードの質量Ａに対する、コードに含まれる液体成分の質量（Ａ－Ｂ）の百分率（{（Ａ－Ｂ）／Ａ｝×１００）を求めて、液体成分の含有率（％）とした。表３及び４に、実施例１～１０及び比較例１～６のゴム補強用コードの液体成分の含有率を示す。 <Content of liquid component>
Within 30 minutes after the heat treatment carried out after immersing the filament bundle in the first aqueous coating agent, a 5 m long cord was sampled from the resulting rubber reinforcing cord. The sample was measured with an electronic balance, and this value was defined as the mass A of the cord. Next, the sample was placed in a dryer heated to 150 ° C. for 30 minutes to remove the solvent in the sample. The difference between the mass A and the mass B was defined as the mass (AB) of the liquid component contained in the cord. The percentage ({(AB) / A} × 100) of the mass (AB) of the liquid component contained in the cord with respect to the mass A of the cord was determined and used as the liquid component content (%). Tables 3 and 4 show the liquid component contents of the rubber reinforcing cords of Examples 1 to 10 and Comparative Examples 1 to 6.
　＜引張強度＞
　各実施例及び比較例のゴム補強用コードについて、一般的に用いられる引張試験機と一般的に用いられるコードグリップとを用いて引張試験を実施し、その際に得られた破断強度を引張強度とした。なお、破断強度は、ＡＳＴＭ７２６９に準拠して測定した。単位はＮ／コードである。表３及び４に、実施例１～１０及び比較例１～６のゴム補強用コードの引張強度を示す。 <Tensile strength>
For the rubber reinforcing cords of each example and comparative example, a tensile test was performed using a commonly used tensile tester and a commonly used cord grip, and the breaking strength obtained at that time was determined as the tensile strength. It was. The breaking strength was measured according to ASTM 7269. The unit is N / code. Tables 3 and 4 show the tensile strengths of the rubber reinforcing cords of Examples 1 to 10 and Comparative Examples 1 to 6.
　＜接着強度＞
　帆布と、ゴム補強用コードと、マトリックスゴムのシートとをこの順に重ね、１６０℃、３０分の条件でプレスをすることによって、接着強度試験用の試験片を作製した。試験片の寸法は、幅２５ｍｍ、長さ１５０ｍｍ、厚さ３ｍｍとした。なお、試験片において、ゴム補強用コードの長さ方向は試験片の長さ方向とほぼ平行であった。マトリックスゴムには、表２に示す組成を有する、水素化ニトリルゴムを主成分とするものを用いた。次に、コードとマトリックスゴムとをそれぞれ掴み、一方を固定し、もう一方をゴム補強用コードの長さ方向に引き剥がし、幅２５ｍｍ当たりの強度を測定した。 <Adhesive strength>
A canvas, a rubber reinforcing cord, and a matrix rubber sheet were stacked in this order, and pressed at 160 ° C. for 30 minutes to prepare a test piece for an adhesive strength test. The dimensions of the test piece were 25 mm in width, 150 mm in length, and 3 mm in thickness. In the test piece, the length direction of the rubber reinforcing cord was substantially parallel to the length direction of the test piece. As the matrix rubber, a material mainly composed of hydrogenated nitrile rubber having the composition shown in Table 2 was used. Next, the cord and the matrix rubber were each gripped, one was fixed, the other was peeled off in the length direction of the rubber reinforcing cord, and the strength per 25 mm width was measured.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１～１０のゴム補強用コードの液体成分の含有率は、０．１～２．０質量％の範囲内であった。一方、比較例１のゴム補強用コードは、熱処理によって第１の被膜中の溶媒及びフィラメント中の水分が完全に除去されていたので、液体成分の含有率は０．１質量％未満であった。比較例２～６のゴム補強用コードでは、液体成分の含有率は２．０質量％を超えていた。換言すると、比較例１のゴム補強用コードは、本発明のゴム補強用コードを得るために想定される熱処理の範囲を超えた過剰な熱処理が施されたものであり、比較例２～６のゴム補強用コードは、本発明のゴム補強用コードを得るために想定される熱処理の範囲に満たない不十分な熱処理が施されたものであった。 The content of the liquid component in the rubber reinforcing cords of Examples 1 to 10 was in the range of 0.1 to 2.0% by mass. On the other hand, in the rubber reinforcing cord of Comparative Example 1, since the solvent in the first film and the moisture in the filament were completely removed by the heat treatment, the liquid component content was less than 0.1% by mass. . In the rubber reinforcing cords of Comparative Examples 2 to 6, the liquid component content exceeded 2.0 mass%. In other words, the rubber reinforcing cord of Comparative Example 1 was subjected to an excessive heat treatment exceeding the range of the heat treatment assumed for obtaining the rubber reinforcing cord of the present invention. The rubber reinforcing cord was subjected to an insufficient heat treatment less than the range of heat treatment envisaged for obtaining the rubber reinforcing cord of the present invention.
　表３に示すように、実施例１～１０のゴム補強用コードでは、引張強度と接着強度とが共に高く、引張強度は５００Ｎ／コード以上、接着強度は１５０Ｎ／２５ｍｍ以上を満たしていた。一方、表４に示すように、比較例１～６のゴム補強用コードでは、引張強度又は接着強度のいずれか一方が低い結果となった。比較例１では引張強度は５００Ｎ／コード未満であり、比較例２～６では接着強度が１５０Ｎ／２５ｍｍ未満であった。接着強度１５０Ｎ／２５ｍｍ以上では、剥離界面には部分的にゴム破壊があり、１５０Ｎ／２５ｍｍ未満では、第１の被膜付近における界面剥離の状態であった。この結果から、第１の被膜の形成後にコード中に残存する液体成分（主に、第１の被膜用水性処理剤の溶媒）の割合は、引張強度や接着強度と相関があることが確認された。 As shown in Table 3, in the rubber reinforcing cords of Examples 1 to 10, both the tensile strength and the adhesive strength were high, the tensile strength was 500 N / cord or more, and the adhesive strength was 150 N / 25 mm or more. On the other hand, as shown in Table 4, in the rubber reinforcing cords of Comparative Examples 1 to 6, either the tensile strength or the adhesive strength was low. In Comparative Example 1, the tensile strength was less than 500 N / cord, and in Comparative Examples 2 to 6, the adhesive strength was less than 150 N / 25 mm. When the adhesive strength was 150 N / 25 mm or more, the peeling interface was partially damaged by rubber, and when it was less than 150 N / 25 mm, the interface was in the vicinity of the first coating. From this result, it was confirmed that the ratio of the liquid component remaining in the cord after the formation of the first coating (mainly the solvent for the first aqueous coating agent) has a correlation with the tensile strength and the adhesive strength. It was.
［実施例１１～２０及び比較例７～１１］
　＜ゴム補強用コードの製造＞
　まず、実施例１～１０及び比較例２～６と同じ方法で、フィラメント束の表面に第１の被膜を形成し、第１の被膜付きのフィラメント束を４０回／ｍの割合でＺ撚りに下撚りし、それを２本束ねて１００回／ｍの割合でＺ撚りに上撚りしたコードを得た。次に、上撚り後のコード上に、以下の表５に示す組成を有する第２の被膜用処理剤を塗布して乾燥させて、第２の被膜を形成した。実施例１～１０及び比較例２～６と同じ方法で作製された上撚り後のコードに第２の被膜を形成して得られたゴム補強用コードを、それぞれ、実施例１１～２０及び比較例７～１１のゴム補強用コードとした。なお、実施例１１～２０及び比較例７～１１において、第２の被膜は、上撚り後のコードに対し１０質量％であった。なお、第２の被膜用処理剤の乾燥は、処理温度１００℃、処理時間２分で実施した。第２の被膜を形成した後の液体成分の含有率は、表６に示すとおり０．５～１．９質量％の範囲内であり、ゴム補強用コードの液体成分に第２の被膜用処理剤の溶媒も含まれていると考えられる。得られたゴム補強用コードについて、液体成分の含有率、引張強度及び接着強度を測定した。液体成分の含有率、引張強度及び接着強度の測定方法は、実施例１～２０及び比較例１～６と同じである。ただし、液体成分の含有率は、第２の被膜用処理剤を塗布した後の熱処理後３０分以内に測定した。これらの結果を、表６及び７に示す。また、表６及び７には、第１の被膜を形成した際の熱処理後３０分以内であって、第２の被膜を形成する前に測定した液体成分の含有率も併せて示す。 [Examples 11 to 20 and Comparative Examples 7 to 11]
<Manufacture of rubber reinforcing cord>
First, in the same manner as in Examples 1 to 10 and Comparative Examples 2 to 6, a first coating is formed on the surface of the filament bundle, and the filament bundle with the first coating is Z-twisted at a rate of 40 times / m. A cord was obtained by twisting the bottom and bundling two of them and twisting them into a Z twist at a rate of 100 turns / m. Next, a second coating agent having the composition shown in Table 5 below was applied onto the cord after twisting and dried to form a second coating. The rubber reinforcing cords obtained by forming the second coating on the cords after twisting produced by the same method as in Examples 1 to 10 and Comparative Examples 2 to 6, were respectively compared with Examples 11 to 20 and Comparative Examples. The rubber reinforcing cords of Examples 7 to 11 were used. In Examples 11 to 20 and Comparative Examples 7 to 11, the second film was 10% by mass with respect to the cord after the upper twist. The drying of the second coating treatment agent was performed at a treatment temperature of 100 ° C. and a treatment time of 2 minutes. The content of the liquid component after forming the second coating is in the range of 0.5 to 1.9% by mass as shown in Table 6, and the second coating treatment is applied to the liquid component of the rubber reinforcing cord. It is thought that the solvent of the agent is also included. About the obtained rubber | gum reinforcement cord, the content rate, tensile strength, and adhesive strength of a liquid component were measured. The liquid component content, tensile strength, and adhesive strength are measured in the same manner as in Examples 1 to 20 and Comparative Examples 1 to 6. However, the content rate of the liquid component was measured within 30 minutes after the heat treatment after applying the second coating agent. These results are shown in Tables 6 and 7. Tables 6 and 7 also show the liquid component content measured within 30 minutes after the heat treatment when the first film is formed and before the second film is formed.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　実施例１１～２０のゴム補強用コードでは、第２の被膜の形成後の液体成分の含有率は、０．５～２．０質量％の範囲内を満たしていた。比較例７～１１のゴム補強用コードは、液体成分の含有率が２質量％を超えていた。換言すると、比較例７～１１のゴム補強用コードは、本発明のゴム補強用コードを得るために想定される熱処理の範囲に満たない不十分な熱処理が施されたものであった。 In the rubber reinforcing cords of Examples 11 to 20, the content ratio of the liquid component after the formation of the second coating satisfied the range of 0.5 to 2.0% by mass. In the rubber reinforcing cords of Comparative Examples 7 to 11, the liquid component content exceeded 2 mass%. In other words, the rubber reinforcing cords of Comparative Examples 7 to 11 were subjected to insufficient heat treatment that did not satisfy the range of heat treatment envisaged for obtaining the rubber reinforcing cord of the present invention.
　表６に示すように、実施例１１～２０のゴム補強用コードでは、引張強度と接着強度とが共に高く、引張強度は５００Ｎ／コード以上、接着強度は２００Ｎ／２５ｍｍ以上を満たしていた。比較例７～１１では、マトリックスゴムとの接着性向上のための第２の被膜が設けられているにも関わらず、接着強度が２００Ｎ／２５ｍｍ未満であった。接着強度２００Ｎ／２５ｍｍ以上では剥離界面がゴム破壊であり、接着強度２００Ｎ／２５ｍｍ未満では、第１の被膜付近における界面剥離の状態であった。すなわち、複数層の被膜が設けられているゴム補強用コードにおいても、ゴム補強用コードに含まれる液体成分の割合は、引張強度や接着強度と相関があることが確認された。 As shown in Table 6, in the rubber reinforcing cords of Examples 11 to 20, both the tensile strength and the adhesive strength were high, the tensile strength was 500 N / cord or more, and the adhesive strength was 200 N / 25 mm or more. In Comparative Examples 7 to 11, the adhesive strength was less than 200 N / 25 mm even though the second coating for improving the adhesion with the matrix rubber was provided. When the adhesive strength was 200 N / 25 mm or more, the peeling interface was rubber fracture, and when the adhesive strength was less than 200 N / 25 mm, the interface was in the vicinity of the first coating. That is, it was confirmed that the ratio of the liquid component contained in the rubber reinforcing cord has a correlation with the tensile strength and the adhesive strength even in the rubber reinforcing cord provided with a plurality of layers of the coating.
　本発明のゴム補強用コードは、マトリクスゴムとの高い接着強度と、高い引張強度とを実現できるので、様々なゴム製品の補強に適用可能である。例えば、耐熱性と耐屈曲疲労性とが高い次元で要求されるタイミングベルトなどの補強用コードとしても好適に利用できる。また、本発明のゴム製品は、高負荷に耐え得ることができるので、様々な用途に適用可能である。 The cord for reinforcing rubber according to the present invention can realize high adhesive strength with a matrix rubber and high tensile strength, and can be applied to reinforcement of various rubber products. For example, it can be suitably used as a reinforcing cord for a timing belt or the like that requires a high level of heat resistance and bending fatigue resistance. Moreover, since the rubber product of this invention can endure a high load, it is applicable to various uses.

Claims (10)

  1. 　ゴム製品を補強するためのゴム補強用コードであって、
    　前記ゴム補強用コードは、少なくとも１つのストランドを備え、
    　前記ストランドは、少なくとも１つのフィラメント束と、前記フィラメント束の少なくとも表面の一部を覆うように設けられた第１の被膜と、
    を含んでおり、
    　前記フィラメント束は、実質的にポリパラフェニレンテレフタルアミド繊維フィラメントからなり、
    　前記第１の被膜は、ゴム成分及び架橋剤を含み、
    　前記ゴム補強用コードは液体成分をさらに含んでおり、前記ゴム補強用コードにおける前記液体成分の含有率が０．１～２．０質量％の範囲内である、
    ゴム補強用コード。     A rubber reinforcing cord for reinforcing a rubber product,
    The rubber reinforcing cord includes at least one strand,
    The strand includes at least one filament bundle, and a first coating provided to cover at least a part of the surface of the filament bundle,
    Contains
    The filament bundle consists essentially of polyparaphenylene terephthalamide fiber filaments,
    The first coating includes a rubber component and a crosslinking agent,
    The rubber reinforcing cord further includes a liquid component, and the content of the liquid component in the rubber reinforcing cord is in the range of 0.1 to 2.0 mass%.
    Cord for rubber reinforcement.
  2. 　前記ゴム補強用コードは、前記第１の被膜上に設けられた第２の被膜をさらに含んでおり、
    　前記ゴム補強用コードにおける前記液体成分の含有率が０．５～２．０質量％の範囲内である、
    請求項１に記載のゴム補強用コード。     The rubber reinforcing cord further includes a second coating provided on the first coating,
    The content of the liquid component in the rubber reinforcing cord is in the range of 0.5 to 2.0% by mass.
    The rubber reinforcing cord according to claim 1.
  3. 　前記ゴム成分が、ニトリルゴム、水素化ニトリルゴム、カルボキシル変性ニトリルゴム及びカルボキシル変性水素化ニトリルゴムからなる群より選ばれる少なくともいずれか１つを含む、
    請求項１又は２に記載のゴム補強用コード。     The rubber component includes at least one selected from the group consisting of nitrile rubber, hydrogenated nitrile rubber, carboxyl-modified nitrile rubber, and carboxyl-modified hydrogenated nitrile rubber.
    The rubber reinforcing cord according to claim 1 or 2.
  4. 　前記架橋剤が、マレイミド系架橋剤及びポリイソシアネートからなる群より選ばれる少なくともいずれか１つを含む、
    請求項１～３のいずれか１項に記載のゴム補強用コード。     The cross-linking agent includes at least one selected from the group consisting of maleimide cross-linking agents and polyisocyanates,
    The rubber reinforcing cord according to any one of claims 1 to 3.
  5. 　前記第１の被膜が、レゾルシン－ホルムアルデヒド縮合物を含まない、
    請求項１～４のいずれか１項に記載のゴム補強用コード。     The first coating does not contain resorcin-formaldehyde condensate;
    The rubber reinforcing cord according to any one of claims 1 to 4.
  6. 　前記第１の被膜の質量が、前記フィラメント束の質量の５～３５％の範囲内である、
    請求項１～５のいずれか１項に記載のゴム補強用コード。     The mass of the first coating is in the range of 5 to 35% of the mass of the filament bundle;
    The rubber reinforcing cord according to any one of claims 1 to 5.
  7. 　前記フィラメント束と前記第１の被膜との間に設けられた樹脂層をさらに含む、
    請求項１～６のいずれか１項に記載のゴム補強用コード。     A resin layer provided between the filament bundle and the first coating;
    The rubber reinforcing cord according to any one of claims 1 to 6.
  8. 　前記樹脂層が、エポキシ樹脂、ポリウレタン樹脂及びイソシアネート化合物からなる群より選ばれる少なくともいずれか１つを含む、
    請求項７に記載のゴム補強用コード。     The resin layer contains at least one selected from the group consisting of an epoxy resin, a polyurethane resin, and an isocyanate compound,
    The rubber reinforcing cord according to claim 7.
  9. 　請求項１～８のいずれか１項に記載のゴム補強用コードで補強されたゴム製品。 A rubber product reinforced with the rubber reinforcing cord according to any one of claims 1 to 8.
  10. 　ゴムマトリックスと、前記ゴムマトリックスに埋設された前記ゴム補強用コードと、を含むゴムベルトである、
    請求項９に記載のゴム製品。
          A rubber belt comprising a rubber matrix and the rubber reinforcing cord embedded in the rubber matrix.
    The rubber product according to claim 9.
PCT/JP2017/015756 2016-04-21 2017-04-19 Rubber-reinforcing cord and rubber product using same WO2017183660A1 (en)

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