WO2022065262A1 - Composition adhésive de caoutchouc à résine, corps composite de cordon de fibres organiques-caoutchouc, et pneu - Google Patents

Composition adhésive de caoutchouc à résine, corps composite de cordon de fibres organiques-caoutchouc, et pneu Download PDF

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WO2022065262A1
WO2022065262A1 PCT/JP2021/034431 JP2021034431W WO2022065262A1 WO 2022065262 A1 WO2022065262 A1 WO 2022065262A1 JP 2021034431 W JP2021034431 W JP 2021034431W WO 2022065262 A1 WO2022065262 A1 WO 2022065262A1
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rubber
adhesive composition
compound
less
mass
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PCT/JP2021/034431
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English (en)
Japanese (ja)
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真明 中村
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株式会社ブリヂストン
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • C09J109/04—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09J139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • 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
    • D06M13/10—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 oxygen
    • D06M13/11—Compounds containing epoxy groups or precursors thereof
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a rubber-resin adhesive composition, a rubber-organic fiber cord composite, and a tire.
  • an organic fiber cord such as a tire cord made of nylon fiber, polyester fiber or the like and a rubber composition for a tire are adhered to form an organic fiber cord-rubber composite. It is done.
  • a method of coating the organic fiber cord with an adhesive composition for an organic fiber cord, embedding it in a rubber composition for a tire, and co-vulcanizing it with the rubber composition for a tire is widely used.
  • a solvent is generally used for the purpose of adjusting the viscosity of the organic fiber cord adhesive composition, but the solvent is used in the step. It is preferable to use water having a small environmental load as the solvent because the solvent volatilizes. Further, when the adhesive composition for organic fiber cords is coated with the adhesive composition for organic fiber cords by dipping, it is necessary to reduce the viscosity until the adhesive composition for organic fiber cords can be applied by dipping.
  • the components contained in the water-based adhesive composition having water-based properties need to have a polar molecular structure.
  • polymer materials such as rubber and organic fiber cord base materials, which are adherends, have low polarity, and are suitable for the surface polarity of rubber, organic fiber cord base materials, etc. and the adhesive composition for organic fiber cords. If the difference from the polarity of the contained components becomes large, it becomes difficult to adhere. Therefore, in order to use the water-based adhesive composition as an adhesive composition for an organic fiber cord, the components contained in the water-based adhesive composition must have polarity because they are aqueous, but this causes the components to have polarity. It is necessary to control the polarity so that there is a difference from the polarity of the adherend and the adhesiveness does not decrease. Therefore, an aqueous adhesive composition for an organic fiber cord having a function of achieving both of these conflicts is preferably used.
  • the adhesive composition for an organic fiber cord is an RFL (resorcin-formaldehyde-latex) adhesive composition obtained by aging a mixed solution containing resorcin, formalin and rubber latex, or the RFL adhesive composition.
  • Adhesive compositions in which a specific adhesion promoter is mixed have been used (see Patent Documents 1 to 4).
  • an adhesive composition consisting of a water-dispersible rubber latex component, a water-based phenol resin obtained by mixing and aging water-soluble resorcin and formalin, and an adhesive composition (patented).
  • Document 1 has been found to have a function of achieving both adhesion to rubber as an adherend and adhesion to a substrate surface having low polarity such as an organic fiber cord material, and is widely used worldwide. Has been done.
  • the rubber latex component contained in the RFL adhesive composition adheres to the adhered rubber side by co-condensation, while the resorcin having adhesiveness to the organic fiber base material is used.
  • the reason why resorcin is preferably used is that the polar functional group introduced into the phenol ring in order to obtain water solubility while providing a phenolic condensed resin which is a resin type having high adhesiveness to the adherend is used. This is because it is a hydroxyl group having a relatively small polarity and is less likely to cause steric hindrance, and can provide a resin component having high adhesiveness to the organic fiber base material side.
  • the RFL adhesive composition can be obtained by mixing and aging resorcin, formaldehyde, and a rubber latex using loginic acid or the like as an emulsifier during polymerization in the presence of a basic composition.
  • the water-soluble resorcin and formaldehyde are condensed by the resole-type condensation reaction under the base (Patent Document 2), and the logoic acid on the surface of the latex is combined with the methylol group at the terminal of the resole-type phenol-formaldehyde addition condensate. It is presumed to be decondensed (Non-Patent Document 1).
  • the latex is crosslinked with the resorcin-formaldehyde condensate via rosin acid to enhance adhesion.
  • the water-based adhesive composition is water-based (water-dispersed) in order to improve the adhesion to the surface of a base material having less polarity such as an organic fiber cord material.
  • Adhesive promoters that are either (s) or water-soluble have been used.
  • water-dispersible adhesive accelerator examples include (blocked) isocyanates such as methylenediphenyldiisocyanate having a particle size of 0.01 to 0.50 ⁇ m (see Patent Document 3), cresol novolac type polyfunctional epoxy resins, and the like. Water-insoluble phenolic / novolak-type resin water-dispersed particles (see Patent Document 4) and the like are used.
  • adhesion promoter containing a water-soluble group examples include a novolak-type condensate sodium hydroxide solution (see Patent Document 5) obtained by a novolak reaction between resorcin and formaldehyde, and novolak of chlorophenols and formaldehyde.
  • Phenolic resins that dissolve in water in the presence of basic substances such as ammonium solutions of type condensates, or aqueous urethane compounds that have a (thermally dissociable blocked) isocyanate group and a self-soluble group (Patent Documents). 6) and the like are used in combination with the RFL adhesive composition.
  • an adhesive composition composed of a rubber latex, a blocked isocyanate compound, an epoxide compound, and an amino compound as a curing agent (see Patent Document 7), or a urethane resin having a (heat-dissociable blocked) isocyanate group, an epoxidized compound, and the like.
  • An adhesive composition for an organic fiber cord containing a polymer having an oxazoline group, a basic catalyst having a number average molecular weight of 1,000 to 75,000, and a rubber latex is an organofiber cord containing no isocyanate. It is disclosed as an adhesive composition for use.
  • the above-mentioned adhesive composition for organic fiber cords containing no resorcin can be crosslinked between the latex component in the coated rubber composition and the resorcin-formaldehyde condensate in the adhesive composition for organic fiber cords. Therefore, there is a problem that the adhesiveness is lowered as compared with the conventional RFL adhesive composition. Further, the adhesive composition for an organic fiber cord containing no resorcin as described above has a problem that the cord strength of the organic fiber cord coated with the adhesive composition for an organic fiber cord is lowered. rice field.
  • the present invention has been made in view of such circumstances. (1) By not using resorcin, the environmental load is small. (2) Good adhesion between the resin (particularly the organic fiber cord) and the coated rubber composition. It is an object of the present invention to provide a rubber-resin-resin adhesive composition (particularly, an adhesive composition for an organic fiber cord) capable of obtaining the above-mentioned effect. Another object of the present invention is to provide an organic fiber cord-rubber composite using an organic fiber cord coated with the rubber-resin adhesive composition, and a tire using the organic fiber cord-rubber composite. do.
  • the present inventor has made extensive studies on the composition of the rubber-resin adhesive composition in order to solve the above problems.
  • a rubber-resin adhesive composition containing (A) a synthetic rubber latex having an unsaturated diene, (B) a polyvinylpyrrolidone-based polymer, and (E) a heat-crosslinkable compound is obtained.
  • A a synthetic rubber latex having an unsaturated diene
  • B a polyvinylpyrrolidone-based polymer
  • E a heat-crosslinkable compound
  • the polyvinylpyrrolidone-based polymer is compatible with other polymers and is used for various purposes as an industrial product due to its properties such as film-forming property and adhesiveness, for example, a system containing resorcin and formaldehyde.
  • a fiber reinforced material that exhibits improved adhesiveness to rubber after being coated with polyvinylpyrrolidone in an RFL adhesive that is a mixture of resorcin, formaldehyde, and latex and coated on the organic fibers of the adherend.
  • a finding capable of providing a pneumatic tire including a tire member composed of the same is disclosed (for example, Japanese Patent Application Laid-Open No. 2009-132383).
  • the rubber-resin adhesive composition of the present invention is (A) Synthetic rubber latex with unsaturated diene, (B) Polyvinylpyrrolidone-based polymer and (E) Thermally crosslinkable compound and It is characterized by including.
  • the rubber-resin adhesive composition of the present invention is By not using (1) resorcin, there are effects that the environmental load is small and (2) the adhesiveness between the resin and the coated rubber composition is good.
  • the rubber-organic fiber cord composite of the present invention is characterized by using an organic fiber cord coated with the above-mentioned rubber-resin adhesive composition.
  • the organic fiber cord-rubber complex of the present invention has the above-mentioned effects (1) and (2).
  • the tire of the present invention is characterized by using the above-mentioned organic fiber cord-rubber composite.
  • the tire of the present invention has the above-mentioned effects (1) and (2).
  • the environmental load is small.
  • a rubber-resin-resin adhesive composition (particularly, an adhesive composition for an organic fiber cord) capable of obtaining the above effect.
  • an organic fiber cord-rubber composite using an organic fiber cord coated with the rubber-resin adhesive composition and a tire using the organic fiber cord-rubber composite can also be provided.
  • the rubber-resin adhesive composition, the organic fiber cord-rubber composite, and the tire of the present invention will be described in detail below based on the embodiments thereof. These descriptions are for the purpose of exemplifying the present invention and do not limit the present invention in any way.
  • the rubber-resin-resin adhesive composition of the present invention (hereinafter, may be referred to as "adhesive composition of the present invention") is used.
  • the rubber-resin adhesive composition of the present invention preferably does not contain resorcin.
  • the ( ⁇ ) thermally crosslinkable compound is (C) an aqueous compound having a (thermally dissociative blocked) isocyanate group, or (D) an epoxide compound.
  • the resin to be adhered to the rubber using the rubber-resin-resin adhesive composition of the present invention is not particularly limited, and various resins can be used. Examples of such a resin include a thermoplastic resin and a thermosetting resin. Further, as the resin of the adherend, more specifically, an organic fiber cord is preferable.
  • the organic fiber cord is used to supplement the strength of rubber articles such as tires.
  • this organic fiber cord is used as a reinforcing material, first, a monofilament cord of a spun organic fiber raw yarn or a twisted cord obtained by twisting a multifilament cord can be used as an organic fiber cord. Then, the organic fiber cord is embedded in the rubber covering the organic fiber cord using an adhesive composition, vulcanized and adhered to form an organic fiber cord-rubber composite, and the organic fiber is formed.
  • the cord-rubber composite can be used as a reinforcing member for rubber articles such as tires.
  • the material of the organic fiber cord is not particularly limited, but is an aliphatic polyamide fiber cord such as polyester, 6-nylon, 6,6-nylon, 4,6-nylon, a protein fiber cord such as an artificial fibroin fiber, and a polyketone.
  • Fiber cords aromatic polyamide fiber cords typified by polynonamethylene terephthalamide, paraphenylene terephthalamide, acrylic fiber cords, carbon fiber cords, resin fiber materials typified by cellulose fiber cords such as rayon and lyocell, or these. It can be used for mixed fiber materials.
  • polyester, 6-nylon, and 6,6-nylon are preferable, and polyester is particularly preferable.
  • the polyester material is a polymer having an ester bond in the main chain, and more specifically, 80% or more of the bonding mode of the repeating unit in the main chain is an ester bonding mode.
  • the polyester are not particularly limited, but are limited to glycols such as ethylene glycol, propylene glycol, butylene glycol, methoxypolyethylene glycol, and pentaerythritol, and terephthalic acid, isophthalic acid, and dimethyl compounds thereof. Examples thereof include those obtained by condensation with a dicarboxylic acid such as an esterification reaction or a transesterification reaction.
  • the most typical polyester is polyethylene terephthalate.
  • the organic fiber cord is preferably an organic fiber cord obtained by twisting a plurality of single fiber filaments, particularly for the purpose of reinforcing rubber articles such as tire articles and conveyor belts. Further, the organic fiber cord is preferably an organic fiber cord obtained by twisting an upper twisted single fiber filament and a lower twisted single fiber filament. In this case, it is more preferable that the twist coefficient of the lower twist is 1,300 or more and 2,500 or less, and / or the twist coefficient of the upper twist is 900 or more and 1,800 or less.
  • the adhesive composition for an organic fiber cord of the present invention contains a rubber latex.
  • the adhesiveness with the rubber member can be enhanced.
  • the above-mentioned "(A) synthetic rubber latex having unsaturated diene" contained in the rubber-resin-resin adhesive composition of the present invention is an adhesive layer made of a rubber-resin adhesive composition. It is a component for adhering to the coated rubber composition which is the adherend thereof.
  • the synthetic rubber latex having (A) unsaturated diene is compatible with the rubber polymer contained in the coated rubber composition which is the adherend, and the unsaturated diene moiety is co-vulcanized to co-vulcanize the rubber. Form vulcanization bond.
  • the rubber-resin-resin adhesive composition of the present invention containing "(A) synthetic rubber latex having unsaturated diene” has good adhesiveness between the resin and the coated rubber composition.
  • the synthetic rubber latex having (A) unsaturated diene is not limited, but is limited to a styrene-butadiene copolymer rubber latex, a vinylpyridine-styrene-butadiene copolymer rubber latex, and a carboxyl group-modified styrene-butadiene.
  • examples thereof include copolymer rubber latex, nitrile rubber latex, and chloroprene rubber latex. These may be used alone or in combination of two or more. Of these, vinyl pyridine-styrene-butadiene copolymer rubber latex is preferable.
  • the vinylpyridine-styrene-butadiene copolymer rubber latex is a rubber latex that has been widely used in articles such as rubber-resin adhesive compositions and tires, and the rubber-resin adhesive composition of the present invention. Also in the resin (particularly, organic fibers) without splitting the adhesive layer due to the advantage of providing a good bond between the adhesive layer and the adherend rubber and being relatively flexible and flexible. This is because it is possible to accompany the deformation of the code).
  • the content (solid content) of the synthetic rubber latex having (A) unsaturated diene is not particularly limited, but is 25 mass. % Or more, and preferably 80% by mass or less. When it is 25% by mass or more, the compatibility between the rubber polymers of the adherend rubber composition and the rubber latex contained in the adhesive composition becomes more appropriate. For example, when an organic fiber cord is used as the resin, the organic fiber This is because the adhered state of the coated rubber in the cord-rubber composite becomes better. From the same viewpoint, the content (solid content content) of the synthetic rubber latex having (A) unsaturated diene is more preferably 35% by mass or more, further preferably 45% by mass or more.
  • the amount of the resin component contained as another component in the adhesive composition can be relatively secured to a certain level or more, and as a result, the cohesive fracture resistance of the adhesive layer can be secured. This is because sufficient adhesiveness can be obtained by ensuring sufficient adhesion and making it difficult for destruction in the adhesive layer to occur.
  • the content (solid content) of the synthetic rubber latex having (A) unsaturated diene is more preferably 75% by mass or less.
  • the synthetic rubber latex having (A) unsaturated diene for example, after dissolving an emulsifier such as potassium loginate in water, the above-mentioned monomer mixture is added thereto, and further, sodium phosphate or the like is added.
  • an electrolyte, peroxides, etc. as an initiator, polymerizing, and then after reaching a predetermined conversion rate, a charge transfer agent is added to terminate the polymerization, and further, by removing the residual monomer.
  • the emulsifier examples include anionic surfactants such as alkali metal salts of fatty acids, alkali metal salts of logonic acid, sodium formaldehyde condensed naphthalene sulfonate, sulfate esters of higher alcohols, alkylbenzene sulfonates and aliphatic sulfonates, or polyethylene glycols.
  • anionic surfactants such as alkali metal salts of fatty acids, alkali metal salts of logonic acid, sodium formaldehyde condensed naphthalene sulfonate, sulfate esters of higher alcohols, alkylbenzene sulfonates and aliphatic sulfonates, or polyethylene glycols.
  • nonionic surfactants such as the alkyl ester type, the alkyl ether type and the alkyl phenyl ether type of the above are used.
  • emulsifiers it is preferable to contain a metal salt of rosin acid, and it can be used alone (only one type), or it can be used in combination with other emulsifiers in combination of two or more.
  • a metal salt of rosin acid In the production of the synthetic rubber latex having (A) unsaturated diene in the examples of the present invention, an alkali metal salt of rosin acid was used alone.
  • Rosinic acid is a mixture of resin acids having a similar chemical structure, mainly composed of tricyclic diterpenes obtained from pine nuts and the like.
  • These resin acids have three ring structures, two double bonds, and one carboxyl group, and the double bond portion is an ester at the methylol terminal of an unsaturated carboxylic acid or resole-type phenol resin and the carboxyl group portion. It has a highly reactive functional group such as carbylic acid.
  • the amount of such an emulsifier used is 0.1 to 8 parts by mass, preferably 1 to 5 parts by mass, based on 100 parts by mass of all the monomers usually used for latex polymerization.
  • a water-soluble initiator such as potassium persulfate, sodium persulfate, ammonium persulfate, a redox-based initiator, or an oil-soluble initiator such as benzoyl peroxide can be used.
  • Potassium persulfate was used in the production of the synthetic rubber latex having (A) unsaturated diene in the examples of the present invention.
  • chain transfer agent examples include monofunctional alkyl mercaptans such as n-hexyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, and t-hexyl mercaptan; 1,10-.
  • monofunctional alkyl mercaptans such as n-hexyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, and t-hexyl mercaptan; 1,10-.
  • Bifunctional mercaptans such as decandiol, ethylene glycol dithioglycolate; trifunctional mercaptans such as 1,5,10-canditrithiol, trimethylolpropanetristhioglycolate; tetrafunctional mercaptans such as pentaerythritol tetrakisthioglycolate.
  • Classes; disulfides; halogen compounds such as carbon tetrachloride, carbon tetrabromide, ethylene bromide; ⁇ -methylstyrene dimer, turpinolene, ⁇ -terpinene, dipentene, allyl alcohol and the like can be used. These may be used alone or in combination of two or more.
  • alkyl mercaptan is preferable, and n-octyl mercaptan and t-dodecyl mercaptan are more preferable.
  • t-dodecyl mercaptan was used.
  • the amount of such a chain transfer agent used is 0.01 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of all the monomers usually used for latex polymerization.
  • antiaging agents such as hindered phenols, silicone-based, higher alcohol-based, mineral oil-based defoaming agents, reaction terminators, antifreeze agents, etc. are added to the latex, if necessary. Agents may be used.
  • the vinylpyridine-styrene-butadiene copolymer rubber latex is a copolymer containing a vinylpyridine-based monomer, a styrene-based monomer, and a conjugated diene-based butadiene monomer as a constituent unit.
  • a ternary copolymer of a vinyl pyridine-based monomer, a styrene-based monomer, and a conjugated diene-based butadiene monomer a vinyl pyridine-based monomer, a styrene-based monomer, and a conjugated diene.
  • Examples thereof include a copolymer containing a based butadiene monomer and another copolymerizable monomer.
  • the vinylpyridine-based monomer includes vinylpyridine and substituted vinylpyridine in which a hydrogen atom in the vinylpyridine is substituted with a substituent.
  • the vinylpyridine compound include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine and the like, and among these, 2 -Vinylpyridine is preferred.
  • These vinyl pyridine-based monomers may be used alone or in combination of two or more.
  • the styrene-based monomer includes styrene and substituted styrene in which a hydrogen atom in the styrene is substituted with a substituent.
  • examples of the styrene-based monomer include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diinopropylstyrene, 2,4-dimethylstyrene, and 4-t.
  • -Butylstyrene, hydroxymethylstyrene and the like can be mentioned, and among these, styrene is preferable.
  • These styrene-based monomers may be used alone or in combination of two or more.
  • conjugated diene-based butadiene monomer examples include aliphatic conjugated butadiene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene, and among these, 1,3-butadiene is preferable. These conjugated diene-based butadiene monomers may be used alone or in combination of two or more.
  • a known method can be used for the synthesis of the vinylpyridine-styrene-butadiene copolymer rubber latex, and specifically, the method described in JP-A-9-78045 according to the study by the inventors of the present application. Can be used. Then, by utilizing these methods, it is possible to give various compositions and intra-particle structures such as copolymers having a uniform or different composition ratio within the same particles of vinylpyridine-styrene-butadiene copolymer rubber latex. ..
  • vinyl pyridine-styrene-butadiene copolymer rubber latex as city products of copolymers having a uniform composition in the same particles, Nipol 2518 manufactured by Nippon Zeon Corporation and Nippon A & L Inc. ) Made of polymer and the like.
  • examples of market products of copolymers having different composition ratios in the same particle include V0658 manufactured by JSR Co., Ltd. All of these can be used as (A) a synthetic rubber latex having an unsaturated diene in the rubber-resin adhesive composition of the present invention.
  • the monomer ratio of vinyl pyridine: styrene: butadiene is not particularly limited, but the copolymer constituting the vinyl pyridine-styrene-butadiene copolymer particles is not particularly limited. It is preferable that the polymer contains a copolymer obtained by polymerizing a monomer mixture composed of 5 to 20% by mass of vinylpyridine, 10 to 40% by mass of styrene, and 45 to 75% by mass of butadiene.
  • the amount of pyridine moiety having a vulcanization promoting effect is appropriate in the rubber component, and when the degree of cross-linking by sulfur is increased, the adhesive strength of the entire adhesive layer is further improved, and is 20% by mass or less. If this is the case, the degree of cross-linking of the rubber does not become overvulcanized, and a hard adhesive can be obtained. Further, when the amount of styrene is 10% by mass or more, the strength of the latex particles and the adhesive layer is sufficient, the adhesive strength is further improved, and when it is 40% by mass or less, the adhesive layer and the adherend rubber are bonded. This is because it also leads to ensuring the adhesive strength while making the co-sulfurization property appropriate.
  • the composition ratio of the monomer mixture of vinylpyridine: styrene: butadiene was set to 15:15:70.
  • the adhesive composition for an organic fiber cord of the present invention contains (B) a polyvinylpyrrolidone-based polymer in addition to (A) the synthetic rubber latex having an unsaturated diene described above.
  • the (B) polyvinylpyrrolidone-based polymer is composed of a homopolymer of N-vinyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and a copolymerizable comonomer thereof. Includes coalescence.
  • a gum-up phenomenon due to adhesion of a rubber component observed in an adhesive liquid containing a rubber latex is observed. It has the effect of suppressing the occurrence of (adhesive stains), can suppress the deterioration of workability and adhesive quality in the process of applying the adhesive, and can realize excellent adhesiveness. Specifically, it becomes a protective colloid in which the (B) polyvinylpyrrolidone-based polymer component is adsorbed on the rubber latex component particles, and the rubber latex particles in the liquid are subjected to mechanical shear input to the adhesive composition liquid.
  • the polyvinylpyrrolidone-based polymer (B) has been conventionally used as a dispersant for dissolving a substance that is difficult to dissolve in water for industrial use, and as a protective layer for dispersed particles. Further, the polyvinylpyrrolidone-based polymer (B) is also known to have an adsorption effect by interacting with a hydroxyl group of polyphenol.
  • the (B) polyvinylpyrrolidone-based polymer is not only a homopolymer of N-vinyl-2-pyrrolidone, but also N-vinyl-2-pyrrolidone and other polymerizable monomers (hereinafter, “another simpler”). It may also be a copolymer containing a "mer"). Examples of other monomers constituting the copolymer include acrylic acid, methacrylic acid, alkyl esters of acrylic acid (methyl acrylate, ethyl acrylate, etc.) and alkyl esters of methacrylic acid (methyl methacrylate, ethyl methacrylate, etc.).
  • Acrylic acid aminoalkyl esters (such as diethylaminoethyl acrylate), methacrylic acid aminoalkyl esters, acrylic acid and glycol monoesters, methacrylic acid and glycol monoesters (such as hydroxyethyl methacrylate), acrylic acid alkali metals Salt, alkali metal salt of methacrylic acid, ammonium salt of acrylic acid, ammonium salt of methacrylic acid, quaternary ammonium derivative of aminoalkyl ester of acrylic acid, quaternary ammonium derivative of aminoalkyl ester of methacrylic acid, diethylaminoethyl acrylate Tertiary ammonium compound with methyl sulphate, vinyl methyl ether, vinyl ethyl ether, alkali metal salt of vinyl sulfonic acid, ammonium salt of vinyl sulfonic acid, styrene sulfonic acid, styrene sulfonate, allyl
  • a step of polymerizing a monomer containing vinylpyrrolidone to form a polymer and an ethylenically unsaturated substance other than vinylpyrrolidone can be produced.
  • a polymer can be obtained by a living radical polymerization method or the like, which comprises a step of polymerizing a monomer containing a monomer to form a polymer.
  • the proportion of the other monomer contained in the (B) polyvinylpyrrolidone-based polymer is preferably 50% or less in terms of mass ratio.
  • the K value (value representing the size of the molecular weight by the fikencher method) of the (B) polyvinylpyrrolidone-based polymer is preferably 10 to 100, more preferably 15 to 60.
  • the K value is a constant representing the degree of polymerization proposed by the German chemist Fikencher (see Zellrose Hemy Vol. 13, pp. 58-64, pp. 71-74 (1932)), and is described above (B).
  • the K value of the polyvinylpyrrolidone-based polymer is less than 10, the action of adsorbing as a protective colloid to the (A) rubber latex component particles contained in the adhesive composition becomes low, and the adhesive liquid is used for gum-up.
  • the number average molecular weight of the (B) polyvinylpyrrolidone-based polymer is preferably 5,000 or more, and more preferably 9,000 or more. Further, the number average molecular weight of the (B) polyvinylpyrrolidone-based polymer is preferably 3,000,000 or less, and more preferably 1,000,000 or less. When the number average molecular weight is 5,000 or more, the effect of improving the adhesiveness between the resin and the coated rubber composition can be easily obtained, and when it is 3,000,000 or less, the viscosity of the adhesive liquid becomes high and it becomes difficult to handle. You can prevent that.
  • the polyvinylpyrrolidone-based polymer (B) can be added to the latex (A) in the state of an aqueous solution to which water is added.
  • the solution containing the vinylpyrrolidone-based polymer and water is prepared by dissolving a reaction solution after the polymerization reaction of the vinylpyrrolidone-based polymer described later, a dried product of the vinylpyrrolidone-based polymer, or the like in a solvent. It means the obtained solution, and hereinafter, this may be referred to as "vinylpyrrolidone-based polymer-containing solution".
  • the content (solid content) of the (B) vinylpyrrolidone-based polymer in the vinylpyrrolidone-based polymer-containing solution is not particularly limited, but is preferably 5 to 50% by weight, preferably 10 to 40% by weight. More preferably, it is by weight%. When it is 5% by weight or more, the production efficiency can be further increased and the cost can be reduced, and when it is 50% by weight or less, the viscosity is suppressed and the workability can be maintained well.
  • the content (solid content content) of the (B) polyvinylpyrrolidone-based polymer is not particularly limited, but is 0.1% by mass. The above is preferable, 1% by mass or more is more preferable, and 3% by mass or more is more preferable. Further, it is preferably 15% by mass or less, and more preferably 10% by mass or less.
  • the content of the (B) polyvinylpyrrolidone-based polymer is 0.1% by mass or more, it is possible to further suppress the adhesion of the adhesive composition for an organic fiber cord to a roll or the like, and the workability is improved. It has the advantage of being better.
  • the content of the (B) polyvinylpyrrolidone-based polymer is 15% by mass or less, the amount contained in the adhesive layer does not become too large, and the fracture resistance of the adhesive layer can be sufficiently secured.
  • the "(heat dissociative blocked) isocyanate group" of the above-mentioned "(C) (aqueous compound having a heat dissociative blocked) isocyanate group” means a heat dissociative blocked isocyanate group or an isocyanate group.
  • aqueous of the "(C) (thermally dissociable blocked) aqueous compound having an isocyanate group indicates that it is water-soluble or water-dispersible, and the water-soluble does not necessarily mean completely water-soluble. It also means that it is partially water-soluble, or that it does not undergo phase separation in the aqueous solution of the adhesive composition of the present invention.
  • the thermally dissociable blocking agent is a blocking agent compound capable of dissociating the blocking agent and restoring the isocyanate group by performing heat treatment as necessary while protecting the isocyanate group from an arbitrary chemical reaction. If there is, it is not particularly limited. Specifically, at the temperature of the heat treatment in which the adhesive treatment liquid is attached and dried and then heat-cured, the heat that can restore the crosslinking reactivity of the isocyanate group whose reactivity is suppressed by being sealed with the heat dissociable blocking agent. It is preferably the dissociation temperature.
  • the blocking agent include alcohol, phenol, active methylene, oxime, lactam, amine and the like, and are not particularly limited.
  • Mercaptans such as acetoanilides and acetate amides; imides such as succinic acid imide, phthalate imide and maleic acid imide; Subsulfates such as sodium bisulfite; Cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazo, 4-bromo-3,5-dimethylpyrazole and 3-methyl- Pyrazoles such as 5-phenylpyrazole; dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dicyclohexylamine, diphenylamine, xylidine, N, N-diethylhydroxyamine, N, N'-diphenylform amidine, 2- Amines such as hydroxypyridine, 3-hydroxy
  • the "(C) (thermally dissociable blocked) aqueous compound having an isocyanate group” specifically contains aromatic polyisocyanates or aromatic aliphatic polyisocyanates, and is used as aromatic isocyanates.
  • aromatic polyisocyanates or aromatic aliphatic polyisocyanates specifically contains aromatic polyisocyanates or aromatic aliphatic polyisocyanates, and is used as aromatic isocyanates.
  • phenylenediocyanates such as m-phenylenedi isocyanate and p-phenylenedi isocyanate
  • tolylene diisocyanates such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI)
  • 2,4'-diphenylmethane diisocyanate, Diphenylmethane diisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI), dialkyldiphenylmethane diisocyanate, te
  • aromatic aliphatic polyisocyanates examples include xylylene diisocyanates such as m-xylylene diisocyanate, p-xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate; diethylbenzene diisocyanate; and ⁇ , ⁇ , ⁇ , ⁇ -tetra. Methylxylylene diisocyanate (TMXDI); and the like.
  • modified products such as carbodiimide, polyol and allophanate of the above-mentioned polyisocyanate can be mentioned.
  • aromatic isocyanates are preferable from the viewpoint of code focusing of the adhesive composition, and more preferably tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or polymethylene. It is a polyphenyl polyisocyanate (polymeric MDI), and particularly preferably diphenylmethane diisocyanate (MDI).
  • the "(C) (heat dissociative blocked) isocyanate group-containing aqueous compound” is not particularly limited, but is more preferably an aqueous urethane compound having a (heat-dissociative blocked) isocyanate group.
  • the details of the aqueous urethane compound having a (heat dissociative blocked) isocyanate group will be described later.
  • the content (solid content content) of the aqueous compound having the (heat dissociative blocked) isocyanate group of (C) is not particularly limited, but is preferably 5% by mass or more, preferably 75% by mass. % Or less is preferable. This is because when the content is 5% by mass or more, the adhesiveness between the resin and the coated rubber composition becomes better. From the same viewpoint, the content (solid content content) of the aqueous compound having the (C) (heat dissociative blocked) isocyanate group is more preferably 10% by mass or more, and more preferably 15% by mass or more. Is even more preferable.
  • the amount of other components such as rubber latex to be blended in the adhesive composition can be relatively secured to a certain level or more, and as a result, the adhesiveness with the adherend rubber can be secured. Is better.
  • the content (solid content content) of the aqueous compound having the (C) (heat dissociative blocked) isocyanate group is more preferably 70% by mass or less, and more preferably 55% by mass or less. Is even more preferable.
  • a polyester synthetic resin material such as polyethylene terephthalate, which is widely used as an organic fiber cord, is composed of a flat linear polymer chain.
  • the surface of the polymer chain or the gaps between the polymer chains have a ⁇ -electronic atmosphere derived from the aromatics and the like contained in the polymer chain.
  • polyester has a particularly small number of hydroxyl groups on the surface as compared with 6,6-nylon. Therefore, conventionally, the adhesive composition for an organic fiber cord used for an organic fiber cord made of polyester has been used in order to obtain sufficient adhesive strength.
  • the adhesive composition for organic fiber cords is dispersed in the gaps between the polymer chains of the organic fiber cords
  • -The adhesive layer of the adhesive composition for organic fiber cords is the polymer chains of the organic fiber cords.
  • Adhesion to the surface For the purpose of this, a molecule having a planar structure (“a portion easily diffused into an organic fiber cord”) having an aromatic ring having an aromatic ⁇ electron on the side surface has been contained as an adhesion promoter.
  • water dispersibility thermalally dissociative blocked
  • Isocyanate compounds have been used.
  • the rubber-resin-resin adhesive composition of the present invention in addition to the hydrophobic aromatic polyisocyanate portion, which is a “portion that easily diffuses into the resin” in the molecular structure, a “part that does not easily diffuse into the resin”. It is more preferable to contain "an aqueous urethane compound having a (thermally dissociable blocked) isocyanate group" which also has a hydrophilic molecular chain portion.
  • aqueous of the “aqueous urethane compound” indicates that it is water-soluble or water-dispersible, and the water-soluble does not necessarily mean completely water-soluble, but is partially water-soluble. Alternatively, it also means that no phase separation occurs in the aqueous solution of the adhesive composition.
  • the "urethane compound" of the "aqueous urethane compound” is a compound having a covalent bond formed between the nitrogen of the amine and the carbon of the carbonyl group, and refers to a compound represented by the following general formula.
  • R and R' represent a hydrocarbon group.
  • the molecular weight of the "aqueous urethane compound having a (heat dissociative blocked) isocyanate group” is not particularly limited as long as it can maintain aqueous properties, but is preferably a number average molecular weight of 1,500 to 100. It is 000, and particularly preferably the number average molecular weight is 9,000 or less.
  • the method for synthesizing the "aqueous urethane compound having a (heat dissociative blocked) isocyanate group” is not particularly limited, but the method described in JP-A-63-51474 and the like can be used. It can be a known method.
  • a preferred embodiment of the above-mentioned "aqueous urethane compound having a (heat dissociative blocked) isocyanate group” is ( ⁇ ) An organic polyisocyanate compound having 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less. ( ⁇ ) A compound having 2 or more and 4 or less active hydrogen groups and having a number average molecular weight of 5,000 or less. A compound having ( ⁇ ) a thermally dissociative blocking agent and ( ⁇ ) at least one active hydrogen group and at least one anionic, cationic or nonionic hydrophilic group.
  • the mixing ratio of each of ( ⁇ ), ( ⁇ ), ( ⁇ ) and ( ⁇ ) to the total amount is Regarding ( ⁇ ), 40% by mass or more, 85% by mass or less, Regarding ( ⁇ ), 5% by mass or more, 35% by mass or less, Regarding ( ⁇ ), 5% by mass or more, 35% by mass or less, and Regarding ( ⁇ ), 5% by mass or more, 35% by mass or less, It is a reaction product after mixing and reacting so that Moreover, when the molecular weight of the isocyanate group (-NCO) is 42, the composition ratio of the (heat dissociative blocked) isocyanate group in the reaction product is 0.5% by mass or more and 11% by mass or less. It is characterized by being.
  • aqueous urethane compound having a (thermally dissociable blocked) isocyanate group is urethane because it has both a moiety composed of a (thermally dissociable blocked) isocyanate group and a hydrophilic moiety having a hydrophilic group. This is because it has the advantage of increasing the self-hydrophilicity of the compound.
  • the organic polyisocyanate compound having ( ⁇ ) 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less is not particularly limited, but is an aromatic polyisocyanate compound and an oligomer thereof. It is preferable, and other aliphatic, alicyclic or heterocyclic polyisocyanate compounds and oligomers thereof may be used.
  • the reaction product after reacting such an organic polyisocyanate compound having ( ⁇ ) 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less is "(thermally dissociable blocked)". This is because the "aqueous urethane compound having an isocyanate group" is more likely to be dispersed in the gaps between the polymer chains of the resin.
  • aliphatic polyisocyanate compound ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecanediisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2 , 4,4-trimethylhexamethylene diisocyanate, dimerate diisocyanate, lysine diisocyanate and the like
  • examples of the alicyclic polyisocyanate compound include cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate.
  • Isophoron diisocyanate 4,4'-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, etc.
  • the compound include a tolylene diisocyanate adduct of 1,3,5-tris (2'-hydroxyethyl) isocyanuric acid
  • examples of the aromatic polyisocyanate compound include m-phenylenedi isocyanate and p-phenylenedi isocyanate.
  • aromatic polyisocyanate compounds are preferable, and methylenediphenyl polyisocyanate, polyphenylene polymethylene polyisocyanate and the like are particularly preferable.
  • Polyphenylene polymethylene polyisocyanate having a number average molecular weight of 2,000 or less is preferable, and polyphenylene polymethylene polyisocyanate having a number average molecular weight of 1,000 or less is particularly preferable.
  • the reaction product after reacting such an organic polyisocyanate compound having ( ⁇ ) 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less is "(thermally dissociable blocked)". This is because the "aqueous urethane compound having an isocyanate group" is more likely to be dispersed in the gaps between the polymer chains of the resin.
  • the compound having ( ⁇ ) 2 or more and 4 or less active hydrogen groups and having a number average molecular weight of 5,000 or less is not particularly limited, but specifically, the following (i) to (vii).
  • Examples include compounds selected from the group consisting of: (I) Multihydric alcohols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
  • Multivalent amine C2-C4 alkylene oxide heavy adducts of polyhydric phenols and amino alcohols, C2-C4 alkylene oxide heavy adducts of C3 and above polyhydric alcohols, An alkylene oxide copolymer of C2 to C4 or an alkylene oxide polymer of C3 to C4.
  • the active hydrogen group means active hydrogen (atomic hydrogen (hydrogen radical)) and active hydrogen when placed under suitable conditions. It refers to a group containing hydrogen that becomes a hydride ion (hydride). Examples of the active hydrogen group include an amino group and a hydroxyl group.
  • At least one active hydrogen group and at least one of the above-mentioned "compound having ( ⁇ ) at least one active hydrogen group and at least one anionic, cationic or nonionic hydrophilic group examples include, but are not limited to, amino sulfonic acids such as taurine, N-methyl taurine, N-butyl taurine and sulfanic acid, and amino carboxylic acids such as glycine and alanine. ..
  • the method for synthesizing the "aqueous urethane compound having a (heat dissociative blocked) isocyanate group" by mixing and reacting the ( ⁇ ), ( ⁇ ), ( ⁇ ), and ( ⁇ ) is particularly limited. However, a known method such as the method described in JP-A-63-51474 can be used.
  • aqueous urethane compound having a (heat dissociative blocked) isocyanate group is the following general formula (1):.
  • A is a residue of the organic polyisocyanate compound from which the active hydrogen group has been eliminated.
  • X is a residue of a polyol compound having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less from which the active hydrogen group has been eliminated.
  • Y is the residue of the heat dissociative blocking agent from which the active hydrogen group has been eliminated.
  • Z is a residue of a compound having at least one active hydrogen group and a group producing at least one salt or a hydrophilic polyether chain from which the active hydrogen group has been eliminated.
  • aqueous urethane compound having a (thermally dissociable blocked) isocyanate group is a urethane compound because it has both a moiety consisting of a (thermally dissociable blocked) isocyanate group and a hydrophilic moiety having a hydrophilic group. This is because it has the advantage of increasing the self-water solubility of.
  • the "organic polyisocyanate compound" of the "residue from which the active hydrogen group has been removed from the organic polyisocyanate compound” A in the formula (1) contains an aromatic ring.
  • the "aqueous urethane compound having a (heat dissociative blocked) isocyanate group” is more easily dispersed in the gaps between the polymer chains of the resin.
  • examples thereof include methylenediphenylpolyisocyanate and polyphenylenepolymethylenepolyisocyanate.
  • Polyphenylene polymethylene polyisocyanate having a number average molecular weight of 6,000 or less is preferable, and polyphenylene polymethylene polyisocyanate having a number average molecular weight of 4,000 or less is particularly preferable.
  • polyol compound having 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less is not particularly limited, but is specifically selected from the group consisting of the following (i) to (vi). Examples include compounds: (I) Multihydric alcohols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
  • aqueous urethane compound having a (heat dissociative blocked) isocyanate group is not particularly limited, but commercially available products such as Elastron BN27, BN77, BN11 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. are used. You can also.
  • the BN77 was used in the following examples herein.
  • One embodiment of the adhesive composition for an organic fiber cord of the present invention comprises (A) a synthetic rubber latex having an unsaturated diene, (B) a polyvinylpyrrolidone-based polymer, and (D) an epoxide compound.
  • the "(D) epoxide compound” refers to a compound having oxacyclopropane (oxylan) (epoxy group), which is a three-membered ring ether, in its structural formula.
  • the "(D) epoxide compound” functions as a cross-linking agent component in the adhesive composition. That is, when the adhesive composition contains “(D) epoxide compound", it is crosslinked between the epoxy group and the hydroxyl group or the like contained in the fiber resin surface, (B) polyvinylpyrrolidone-based polymer or other formulations. Is introduced, and the improvement of the breakage resistance of the adhesive layer and the significant performance improvement in the adhesive force at high temperature can be seen.
  • the "(D) epoxide compound” is mixed with the "(C) (thermally dissociative blocked) aqueous compound having an isocyanate group” and heated.
  • the adhesive composition mainly composed of urethane bonds is obtained.
  • the epoxy group of the "(D) epoxide compound” is preferably polyfunctional. This is because the effect of the suppression is enhanced, the destructive drag of the adhesive layer by the adhesive composition is further enhanced, and the adhesive force at a high temperature is also enhanced.
  • the "(D) epoxide compound” is preferably a compound containing two or more epoxy groups in one molecule. Particularly preferably, it is a compound containing four or more epoxy groups in one molecule. The reason for this is that the epoxy group becomes polyfunctional, and as described above, the destructive drag of the adhesive layer by the adhesive composition is further increased, and the adhesive force at high temperature is also higher.
  • (D) epoxide compound examples include diethylene glycol / diglycidyl ether, polyethylene / diglycidyl ether, polypropylene glycol / diglycidyl ether, neopentyl glycol / diglycidyl ether, and 1,6-hexanediol.
  • Polyhydric alcohols such as diglycidyl ether, glycerol / polyglycidyl ether, trimethylolpropane / polyglycidyl ether, polyglycerol / polyglycidyl ether, pentaerythiol / polyglycidyl ether, diglycerol / polyglycidyl ether, sorbitol polyglycidyl ether, etc.
  • the reaction product with epichlorohydrin; novolak type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin; bisphenol A type epoxy resin and the like.
  • a reaction product of polyhydric alcohols and epichlorohydrin, or a novolak type epoxy resin is preferable.
  • the sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, and novolak type epoxy resin commercially available chemicals can be used.
  • the "(D) epoxide compound” can be used by dissolving it in water or dispersing it in water by emulsification.
  • the "(D) epoxide compound” can be dissolved in water as it is.
  • the above-mentioned “(D) epoxide compound” is dissolved in a small amount of solvent as needed, and the solution is used as a known emulsifier (for example, sodium alkylbenzene sulfonic acid, sodium dioctylsulfosuccinate salt, nonylphenolethylene oxide adduct).
  • Etc. can be emulsified into water to form an emulsified solution.
  • the content (solid content content) of the "(D) epoxide compound” is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.4% by mass or more. It is particularly preferably 1.0% by mass. Further, it is preferably 40% by mass or less, more preferably 30% by mass or less. This is because when the content is 0.1% by mass or more, the adhesiveness between the resin and the coated rubber composition becomes better. Further, if it is 40% by mass or less, the amount of other components such as rubber latex to be blended in the adhesive composition can be relatively secured to a certain level or more, and as a result, the adhesiveness with the adherend rubber can be secured. Is better.
  • the rubber-resin adhesive composition of the present invention is (A) Synthetic rubber latex with unsaturated diene, (B) Polyvinylpyrrolidone-based polymer and It is characterized by containing the (E) thermally crosslinkable compound.
  • the (E) heat-crosslinkable compound contains (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group or (D) an epoxidized compound, and the adhesive composition is produced.
  • Compounds or (D) epoxidized compounds can be mixed in any order.
  • the adhesive composition is applied to the resin coating treatment as soon as possible. Specifically, it is more preferable that the adhesive composition is subjected to a resin coating treatment within 1 to 2 days after mixing the "(D) epoxide compound” with water.
  • the adhesive composition of the present invention is not particularly limited, but for example, after dissolving "(B) a polyvinylpyrrolidone-based polymer" in water, "(A) a synthetic rubber having an unsaturated diene” is used. It can be produced by mixing with “latex”, cooling, and further mixing with "(C) an aqueous compound having a (heat-dissociable blocked) isocyanate group” or (D) an epoxide compound.
  • "(B) a polyvinylpyrrolidone-based polymer” is dissolved in water and then mixed with "(A) a synthetic rubber latex having an unsaturated diene” or (D) an epoxide compound, and further. It can be produced by mixing with "(C) an aqueous compound having a (thermally dissociable blocked) isocyanate group”.
  • the mixed mass ratio [(A): (B)] of "(A) synthetic rubber latex having unsaturated diene” and "(B) polyvinylpyrrolidone-based polymer” is particularly high. Although not limited, it is preferably in the range of 100: 0.1 to 100: 25, more preferably in the range of 100: 0.2 to 100:15 (including the mixed mass ratio at both ends). ). If the mixed mass ratio is 100: 0.1 or more (if the ratio value is 1000 or less), "(B) polyvinylpyrrolidone-based weight" is surrounded by "(A) synthetic rubber latex having unsaturated diene". This is because "coalescence" can be bridged.
  • the mixed mass ratio is 100:25 or less (if the ratio value is 10 or more), "(B) polyvinyl” formed around "(A) synthetic rubber latex having unsaturated diene” is formed.
  • Cross-linking by "pyrrolidone-based polymer” does not become excessive, the adhesive composition layer coated on the resin surface does not become too hard, and the material deterioration of the adhesive composition under repeated strain due to rotation during tire running is small. This is because the adhesiveness can be suitably maintained.
  • the mass ratio [(A): (E)] with the compound is preferably in the range of 100: 5 to 100: 300, more preferably in the range of 100: 15 to 100: 150, and 100: It is even more preferably in the range of 20 to 100: 80 (including the mixed mass ratio at both ends). If the mixed mass ratio is 100: 5 or more (if the ratio value is 20 or less), the ratio of "(A) synthetic rubber latex having unsaturated diene" in the adhesive composition becomes too large. This is because the destructive resistance of the adhesive layer due to the adhesive composition can be sufficiently maintained, and the deterioration of the adhesiveness under strain can be prevented.
  • the ratio occupied by "(A) synthetic rubber latex having unsaturated diene" in the adhesive composition if the mixed mass ratio is 100: 300 or less (if the ratio value is 1/3 or more), the ratio occupied by "(A) synthetic rubber latex having unsaturated diene" in the adhesive composition. Is not too low, and when the coated rubber composition which is the adherend of the resin and the adhesive composition are co-sulfurized and adhered, the coated rubber composition which is the adherend and the above-mentioned "(A) This is because the "synthetic rubber latex having an unsaturated diene" is well compatible with the "synthetic rubber latex", and as a result, the adhesiveness between the coated rubber composition which is the adherend and the adhesive composition is sufficiently high. Is.
  • the (A) synthetic rubber latex having an unsaturated diene, (B) a polyvinylpyrrolidone-based polymer, and (E) a heat-crosslinkable compound are preferably aqueous. This is because water, which is less polluting to the environment, can be used as a solvent.
  • Organic fiber cord-rubber complex The organic fiber cord-rubber complex of the present invention will be described in detail with reference to FIG.
  • FIG. 1 is a schematic cross-sectional view showing an example of the organic fiber cord-rubber complex of the present invention in an embodiment of the present invention.
  • the organic fiber cord-rubber composite 31 the outer radial outer surface of the organic fiber cord 1 is covered with the adhesive layer 32 by the rubber-resin adhesive composition 2 of the present invention. Then, the organic fiber cord 1 is further adhered to the coated rubber composition 33 located on the outer radial side thereof via the adhesive 32 by the rubber-resin adhesive composition 2, and the organic fiber cord 1 of the present invention is formed.
  • -Rubber composite 31 is formed.
  • the form of the rubber reinforcing material using the rubber-resin adhesive composition of the present invention may be a film, a short fiber, a non-woven fabric, or the like in addition to the organic fiber cord-rubber composite. ..
  • the coated rubber composition constituting the organic fiber cord-rubber composite of the present invention preferably contains a rubber component mixed with a compounding agent usually used in the rubber industry.
  • the rubber component is not particularly limited, and for example, in addition to natural rubber, polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), and acrylonitrile butadiene rubber (NBR).
  • Chloroprene rubber (CR), butyl rubber (IIR) and other conjugated diene synthetic rubbers, as well as ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), polysiloxane rubber and the like.
  • EPM ethylene-propylene copolymer rubber
  • EPDM ethylene-propylene-diene copolymer rubber
  • polysiloxane rubber and the like.
  • natural rubber and conjugated diene-based synthetic rubber are preferable. Further, these rubber components may be used alone or in combination of two or more.
  • the organic fiber cord-rubber composite of the present invention covers the organic fiber cord with the rubber-resin-resin adhesive composition according to the present invention to form an adhesive layer, and is contained in the rubber-resin-resin adhesive composition. It is produced by co-vulcanizing and adhering "(A) a synthetic rubber latex having an unsaturated diene" and a rubber component in a coated rubber composition which is an adherend of the organic fiber cord.
  • the method for coating the organic fiber cord with the rubber-resin adhesive composition according to the present invention is not particularly limited, but the organic fiber cord is immersed in the rubber-resin adhesive composition.
  • a method of applying the rubber-resin adhesive composition to the organic fiber cord with a brush, a method of spraying the rubber-resin adhesive composition onto the organic fiber cord, and the like, which are appropriate as necessary. Method can be selected.
  • the organic fiber cord is coated with the rubber-resin adhesive composition
  • the rubber-resin adhesive composition if the rubber-resin adhesive composition is dissolved in various solvents to reduce the viscosity, the coating becomes easier.
  • the solvent for lowering the viscosity of the rubber-resin adhesive composition is environmentally preferable to be mainly composed of water.
  • the thickness of the adhesive layer of the rubber-resin-resin adhesive composition is not particularly limited, but is preferably 50 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 30 ⁇ m or less. preferable. It should be noted that when the amount of the adhesive composition adhered by the adhesive treatment becomes large, the adhesive durability under the rolling of the tire tends to decrease. The reason for this is that the adhesive composition at the interface of the fiber material to be adhered has relatively small deformation due to the stress due to strain due to the high rigidity of the fiber material, but the deformation due to strain increases as the distance from the interface increases. This is to become.
  • the adhesive composition contains a large amount of thermosetting condensate as compared with the adherend rubber material, it is hard and brittle, so that the adhesive fatigue under repeated strain tends to increase.
  • the average thickness of the adhesive composition layer is preferably 50 ⁇ m or less, more preferably 0.5 ⁇ m or more and 30 ⁇ m or less.
  • the concentration of the rubber-resin adhesive composition impregnated in the organic fiber cord is not particularly limited, but is 5.0% by mass or more with respect to the mass of the organic fiber cord. It is preferably 0% by mass or less, and more preferably 7.5% by mass or more and 20.0% by mass or less (both are solid content conversion values).
  • the organic fiber cord coated with the rubber-resin adhesive composition is, for example, dried at a temperature of 100 ° C. or higher and 210 ° C. or lower, and then the glass transition temperature (typically) of the polymer chain of the organic fiber cord. It is preferable to perform the heat treatment at a temperature of [melting temperature: ⁇ 70 ° C.]) or higher and [melting temperature: ⁇ 10 ° C.] or lower) of the polymer chain.
  • the preferred reason for this is that when the temperature is equal to or higher than the glass transition temperature of the polymer chain of the organic fiber cord, the molecular mobility of the polymer chain of the organic fiber cord becomes good, and the rubber-resin adhesive composition
  • the rubber-resin adhesive composition and the organic fiber cord are used so that the adhesion promoter (( ⁇ ) thermally crosslinkable compound) and the polymer chain of the organic fiber cord can sufficiently interact with each other. This is because a sufficient adhesive force between them can be obtained.
  • the organic fiber cord may be pretreated by electron beam, microwave, corona discharge, plasma treatment or the like in advance.
  • the resin material may be in any form such as a film, a cord, a cable, a filament, a filament tip, a cord woven fabric, and a canvas.
  • a cord formed by twisting a plurality of filaments of the resin is preferably used for reinforcing rubber articles such as tire articles and conveyor belts.
  • the synthetic fiber has an upper twist and a lower twist, the twist coefficient of the lower twist is 1,300 to 2,500, and the twist coefficient of the upper twist is 900 to 1,800. ..
  • the organic fiber cord is a polyethylene terephthalate tire cord having a twist structure of 1670 dtex / 2, an upper twist number of 40 times / 10 cm, and a lower twist number of 40 times / 10 cm. It is preferable that the rubber-resin-resin adhesive composition is attached to the organic fiber cord-rubber composite with respect to the mass.
  • the organic fiber cord coated with the rubber-resin adhesive composition is formed by the synthetic rubber latex having (A) unsaturated diene in the rubber-resin adhesive composition and the cover of the organic fiber cord. It is co-vulcanized and adhered to the rubber component in the coated rubber composition which is the adherend.
  • sulfur for example, sulfur, tetramethyltylalium disulfide, dipentamethylenetylalium tetrasulfide and other tyralium polysulfide compounds, 4,4-dithiomorpholin, p-quinone, etc.
  • examples thereof include organic vulcanizers such as dioxime, p, p'-dibenzoquinone dioxime, and cyclic sulfur imide. Above all, it is preferable to use sulfur.
  • the rubber component in the coated rubber composition contains various compounds such as fillers such as carbon black, silica, and aluminum hydroxide, which are usually used in the rubber industry, vulcanization accelerators, antiaging agents, and softeners.
  • the agent can be appropriately blended.
  • the vulcanizing agent contained in the adherend of the synthetic resin material such as the organic fiber cord and / or the adherend of the coated rubber composition is the rubber-resin.
  • the rubber-resin adhesive composition is crosslinked by the vulcanizing agent that has been transferred to the inter-adhesive composition, the effect of adhesion can be obtained. stomach.
  • the tire of the present invention uses the organic fiber cord-rubber composite of the present invention.
  • the rubber-resin-resin adhesive composition of the present invention and the organic fiber cord-rubber composite of the present invention can be applied not only to the above-mentioned tires but also to all rubber articles such as conveyor belts, belts, hoses, and air springs. Can also be applied.
  • (A) vinylpyridine-styrene-butadiene copolymer latex as the synthetic rubber latex having an unsaturated diene is based on Comparative Example 1 described in JP-A-9-78045. Then, it was prepared and used as follows. 130 parts by mass of deionized water and 4.0 parts by mass of potassium rosinate were charged and dissolved in a nitrogen-substituted autoclave having a capacity of 5 liters.
  • a monomer mixture having a composition of 15 parts by mass of vinylpyridine monomer, 15 parts by mass of styrene, and 70 parts by mass of butadiene and 0.60 parts by mass of t-dodecyl mercaptan were charged and emulsified. Then, the temperature was raised to 50 ° C., 0.5 part by mass of potassium persulfate was added, and polymerization was started. After the reaction rate of the monomer mixture reached 90%, 0.1 part by mass of hydroquinone was added to terminate the polymerization. Next, the unreacted monomer was removed under reduced pressure to obtain a vinylpyridine-styrene-butadiene copolymer latex having a solid content concentration of 41% by mass.
  • (B) Polyvinylpyrrolidone-based polymer aqueous solution In the following comparative examples and examples, as the (B) polyvinylpyrrolidone-based polymer, Pitzcol K-30L (polyvinylpyrrolidone, K value 30, weight average molecular weight: 45,000, 30% aqueous solution, Dai-ichi Kogyo Seiyaku Co., Ltd. Made) was used as it was.
  • ((D) Epoxide compound) In the following comparative examples and examples, as the (D) epoxide compound, the trade name "Denacol EX-614B" manufactured by Nagase Chemtech Co., Ltd., which is a sorbitol polyglycidyl ether, (molecular weight: 949, epoxy equivalent: 173, (Solid content concentration: 100% by mass) was diluted with deionized water to produce an aqueous solution having a solid content concentration of 10% by mass, and the aqueous solution was used for preparing the adhesive composition.
  • the trade name "Denacol EX-614B” manufactured by Nagase Chemtech Co., Ltd. which is a sorbitol polyglycidyl ether, (molecular weight: 949, epoxy equivalent: 173, (Solid content concentration: 100% by mass) was diluted with deionized water to produce an aqueous solution having a solid content concentration of 10% by mass, and the aqueous solution was used
  • Latex Adhesive Composition (Comparative Example 1)
  • the synthetic rubber latex having (A) unsaturated diene and water were mixed by adjusting the amount so that the solid content concentration was 18% by mass, and then sufficiently stirred to obtain a latex adhesive composition (A). Comparative Example 1) was obtained.
  • Latex-Aqueous Urethane Adhesive Composition (Comparative Example 2)> The synthetic rubber latex having (A) unsaturated diene and the aqueous compound having (C) (thermally dissociable blocked) isocyanate group are blended as shown in Table 1, and the solid content of the adhesive composition is blended. After adjusting the amount with water so that the concentration became 18% by mass and mixing, the mixture was sufficiently stirred to obtain a latex-aqueous urethane adhesive composition (Comparative Example 2).
  • Latex-Epoxide Compound Adhesive Composition (Comparative Example 3)
  • the synthetic rubber latex having (A) unsaturated diene and the (D) epoxide compound are blended as shown in Table 1, and the adhesive composition is mixed with water so that the solid content concentration is 18% by mass. After adjusting the amount and mixing, the mixture was sufficiently stirred to obtain a latex-epoxide compound adhesive composition (Comparative Example 3).
  • Adhesive Composition (Examples 1 and 2)> As shown in Table 1, each predetermined (A) synthetic rubber latex having an unsaturated diene, (B) a polyvinylpyrrolidone-based polymer, and (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group (Example). The 1) or (D) epoxide compound (Example 2) was blended in this order, adjusted in amount with water so that the solid content concentration of the adhesive composition was 18% by mass, and then mixed. The mixture was sufficiently stirred to obtain an adhesive composition (Examples 1 and 2) according to an embodiment of the present invention.
  • ⁇ Tire code-Making rubber complex As the organic fiber cord, a tire cord made of polyethylene terephthalate having a twist structure of 1670 dtex / 2, an upper twist number of 40 times / 10 cm, and a lower twist number of 40 times / 10 cm was used.
  • the tire cord was immersed in the adhesive compositions of Comparative Examples 1 to 3 and Examples 1 and 2, and the concentration of the adhesive composition impregnated in the tire cord was based on the mass of the organic fiber cord. It was adjusted to 3.8% by mass. Then, after drying (150 ° C., 60 seconds), it was subjected to adhesive heating (240 ° C., 0.8 kg / piece, 60 seconds) and coated with the adhesive compositions of Comparative Examples 1 to 3 and Examples 1 and 2.
  • the tire cord obtained as described above was embedded in an unvulcanized compounded rubber composition and co-vulcanized at 160 ° C. for 20 minutes to prepare a sample tire cord-rubber composite.
  • the unvulcanized rubber composition for coating a rubber composition containing natural rubber, styrene-butadiene rubber, carbon black, vulcanized chemicals and the like was used.
  • Table 1 below shows the formulations of the adhesive compositions of Comparative Examples 1 to 3 and Examples 1 and 2 and the results of the adhesiveness evaluation.
  • A1 Vinyl pyridine latex, vinyl pyridine-styrene-butadiene copolymer latex synthesized by the above method, solid content concentration: 41% by mass.
  • B1 Polyvinylpyrrolidone, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Pitzcol K-30L", number average molecular weight 45,000, K value 27-33, solid content concentration 30% by mass.
  • the present invention (1) By not using resorcin and formaldehyde, the environmental load is small. (2) Good adhesion between the organic fiber cord and the coated rubber composition, A rubber-resin-resin adhesive composition capable of obtaining the above-mentioned effect is provided. In addition, an organic fiber cord-rubber composite using an organic fiber cord coated with the rubber-resin adhesive composition and a tire using the organic fiber cord-rubber composite are also provided. Therefore, the present invention can be used in the industrial field of manufacturing rubber articles such as tires.
  • Organic fiber cord 2 Rubber-resin adhesive composition 31: Organic fiber cord-rubber composite 32: Adhesive layer with rubber-resin adhesive composition 33: Covered rubber composition

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Le but de la présente invention est de fournir une composition adhésive de caoutchouc à résine (plus particulièrement, une composition adhésive de cordon de fibres organiques) dans laquelle (1) la charge environnementale est faible en raison de l'absence d'utilisation de résorcine, et (2) l'adhérence entre une résine (plus particulièrement, un câble de fibres organiques) et une composition de caoutchouc de revêtement est bonne.　Afin de résoudre ce problème, la présente invention est caractérisée en ce qu'elle comprend : (A) un latex de caoutchouc synthétique ayant un diène insaturé ; (B) un polymère de polyvinylpyrrolidone ; et (E) un composé thermiquement réticulable.
PCT/JP2021/034431 2020-09-24 2021-09-17 Composition adhésive de caoutchouc à résine, corps composite de cordon de fibres organiques-caoutchouc, et pneu WO2022065262A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009132383A (ja) * 2007-11-30 2009-06-18 Goodyear Tire & Rubber Co:The 空気入りタイヤ
JP2010255153A (ja) * 2009-04-28 2010-11-11 Bridgestone Corp 有機繊維コード用接着剤組成物、並びにそれを用いたゴム補強材、タイヤおよび接着方法
JP2011069020A (ja) * 2009-09-25 2011-04-07 Bridgestone Corp 有機繊維コード用接着剤組成物、並びにそれを用いたゴム補強材、タイヤおよび接着方法
JP2012224962A (ja) * 2011-04-20 2012-11-15 Bridgestone Corp 有機繊維コード用接着剤組成物、並びにそれを用いたゴム補強材、タイヤおよび接着方法
JP2013064037A (ja) * 2011-09-15 2013-04-11 Bridgestone Corp 有機繊維コード用接着剤組成物及びそれを用いた接着方法、並びにゴム補強材及びタイヤ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009132383A (ja) * 2007-11-30 2009-06-18 Goodyear Tire & Rubber Co:The 空気入りタイヤ
JP2010255153A (ja) * 2009-04-28 2010-11-11 Bridgestone Corp 有機繊維コード用接着剤組成物、並びにそれを用いたゴム補強材、タイヤおよび接着方法
JP2011069020A (ja) * 2009-09-25 2011-04-07 Bridgestone Corp 有機繊維コード用接着剤組成物、並びにそれを用いたゴム補強材、タイヤおよび接着方法
JP2012224962A (ja) * 2011-04-20 2012-11-15 Bridgestone Corp 有機繊維コード用接着剤組成物、並びにそれを用いたゴム補強材、タイヤおよび接着方法
JP2013064037A (ja) * 2011-09-15 2013-04-11 Bridgestone Corp 有機繊維コード用接着剤組成物及びそれを用いた接着方法、並びにゴム補強材及びタイヤ

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