WO2022137908A1 - Composition adhésive pour fibres organiques, corps composite fibres organiques-caoutchouc et pneu - Google Patents

Composition adhésive pour fibres organiques, corps composite fibres organiques-caoutchouc et pneu Download PDF

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Publication number
WO2022137908A1
WO2022137908A1 PCT/JP2021/042296 JP2021042296W WO2022137908A1 WO 2022137908 A1 WO2022137908 A1 WO 2022137908A1 JP 2021042296 W JP2021042296 W JP 2021042296W WO 2022137908 A1 WO2022137908 A1 WO 2022137908A1
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adhesive composition
compound
mass
organic
less
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PCT/JP2021/042296
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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
    • 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
    • C09J109/10—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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
    • 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
    • C09J197/00—Adhesives based on lignin-containing materials
    • 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
    • D06M13/10—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
    • D06M13/152—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 having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/15—Proteins or derivatives 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
    • 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

Definitions

  • the present invention relates to an adhesive composition for organic fibers (hereinafter, also simply referred to as "adhesive composition”), an organic fiber-rubber composite, and a tire.
  • an organic fiber such as a tire cord made of nylon fiber or polyester fiber and a rubber composition such as a rubber composition for a tire are adhered to each other to form an organic fiber-rubber composite.
  • the body is being done.
  • a method of coating an organic fiber with an adhesive composition, embedding it in a rubber composition, and co-vulcanizing with the rubber composition is widely used.
  • a solvent is generally used for the purpose of adjusting the viscosity of the adhesive composition, but since the solvent volatilizes in the step, it is used as the solvent. It is preferable to use water having a small environmental load. Further, when the cord of the organic fiber or the like is coated with the adhesive composition by dipping, it is necessary to make the viscosity low enough to apply the adhesive composition by dipping.
  • the components contained in an aqueous adhesive composition having the property of being soluble or dispersed in water need to have a molecular structure having polarity.
  • polymer materials such as rubber and organic fiber cord base material as an adherend have low polarity, and the polarity of the surface of rubber and organic fiber cord base material and the polarity of the components contained in the adhesive composition. The larger the difference with, the more difficult it is to bond. Therefore, in order to use the water-based adhesive composition as an adhesive composition for rubber articles, the components contained in the water-based adhesive composition need to have polarity because they are water-based.
  • a water-based adhesive composition having a function of achieving both of these contradictory requirements is preferably used.
  • the organic fiber cord 1 is unwound from the unwinding roll, transported by the roll, and in the dipping bath (dipping tank) 3 containing the adhesive composition 2 for the organic fiber cord, the above-mentioned adhesive composition for organic fibers is used. Immersed in object 2.
  • the organic fiber cord 4 coated with the organic fiber adhesive composition 2 is pulled up from the dipping bathtub 3, and the excess organic fiber adhesive composition 2 is removed by the drawing roll 5.
  • the organic fiber cord 4 coated with the adhesive composition 2 for organic fibers is further conveyed by a roll and dried in the drying zone 6, and in the hot zone 7, the resin is thermally cured while being stretched by applying tension.
  • the resin is thermally cured while being standardized (normalized) by accurately adjusting the above tension so as to obtain the desired strong elongation physical properties, and after being air-cooled outside the zone, the take-up roll is used. It is taken up by. In this way, the organic fiber cord is coated with the adhesive composition.
  • the above-mentioned adhesive composition is conventionally an RFL (resorcin-formaldehyde-latex) adhesive composition obtained by aging a mixed solution containing resorcin, formaldehyde and rubber latex, or a specific RFL adhesive composition.
  • Adhesive compositions mixed with adhesion promoters 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 formaldehyde, 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, and is widely used worldwide.
  • a phenolic resin composed of a condensate of resorcin and formaldehyde, which adheres to the adherend rubber side by co-sulfurization with a rubber latex component and has adhesiveness to an organic fiber base material. Depending on the component, it adheres to the adherend base material side.
  • resorcin is preferably used is that it is possible to provide a phenolic condensed resin which is a resin type having high adhesiveness to an adherend, and a polar functional group introduced into a phenol ring in order to obtain water solubility.
  • a resin component which is a hydroxyl group having a relatively small polarity and is less likely to cause steric obstacles and has high adhesiveness to the organic fiber base material side.
  • the RFL adhesive composition is obtained by mixing resorcin, formaldehyde, and a rubber latex using rosinic acid or the like as an emulsifier at the time of polymerization in the presence of a basic composition and aging. ..
  • the water-soluble resorcin and formaldehyde are condensed by the resole-type condensation reaction under the base (see Patent Document 2), and the rosinic acid on the surface of the latex is the methylol group at the end of the resole-type phenol-formaldehyde addition condensate.
  • Patent Document 2 See Non-Patent Document 1.
  • the latex is crosslinked with the resole-type resorcin-formaldehyde condensate via logonic acid to enhance adhesion, and the latex is combined with an aqueous resin to form a encapsulated protective colloid, as shown in FIG.
  • the rubber adhesiveness of the latex is suppressed, so that the stain due to the adhesion of the adhesive composition to the apparatus is reduced.
  • the adhesion promoter added to the RFL adhesive composition is water-based, that is, water, in order to improve the adhesion to the surface of a base material having less polarity, such as an organic fiber cord material, by using an aqueous adhesive composition.
  • Adhesive promoters having the property of being able to dissolve or disperse in 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 resin, and the like. Water-insoluble phenolic / novolak-type resin water-dispersed particles (see Patent Document 4) and the like are used.
  • a novolak-type condensate sodium hydroxide solution obtained by novolacizing reaction of resorcin and formaldehyde, chlorophenols and formaldehyde Phenolic resins that dissolve in water in the presence of basic substances such as a novolak-type condensate ammonium solution, or aqueous urethane compounds that have a (thermally dissociable blocked) isocyanate group and a self-soluble group (patented).
  • Refer to Document 6 and the like are used in combination with the RFL adhesive composition.
  • an adhesive composition consisting of a rubber latex, a blocked isocyanate compound, an epoxide compound, and an amino compound of a curing agent (see Patent Document 7), or a urethane resin having a (heat-dissociable blocked) isocyanate group, an epoxide.
  • An adhesive composition for an organic fiber cord containing a compound, 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 does not contain isocyanate. It is known as an adhesive composition.
  • the adhesive composition containing no resorcin as described above when used, the adhesiveness of the rubber latex, which is measured as an index of the mechanical stability of the adhesive liquid under shear strain, becomes high.
  • the rolls of the drawing roll 5 and the drying zone 6 and the like are used.
  • a new problem has arisen in which the adhesive composition 2 for organic fibers adheres more and the workability of the process deteriorates.
  • the adhesiveness tends to decrease because the surface of the adhesive coating is roughened by adhesion to the above-mentioned device, and further, the latex component and the adhesive composition in the coating rubber composition are likely to be deteriorated. Since cross-linking with the resorcin / formaldehyde condensate in the product cannot be obtained in the first place, there is also a problem that the adhesiveness is lowered as compared with the conventional RFL adhesive composition.
  • the adhesive composition containing no resorcin as described above has a problem that the cord strength of the organic fiber cord coated with the adhesive composition is lowered.
  • an object of the present invention is an adhesive composition for organic fibers, an organic fiber, which can secure desired adhesiveness without using resorcin, is excellent in environmental friendliness, and does not impair workability during use. To provide rubber composites and tires.
  • the present inventor has conducted extensive research on the composition of the adhesive composition for organic fibers in order to solve the above problems.
  • one of (A) a predetermined rubber latex, (B) casein, (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group, (D) an epoxide compound, and (E) a polyphenol.
  • A a predetermined rubber latex
  • B casein
  • C an aqueous compound having a (heat-dissociable blocked) isocyanate group
  • D an epoxide compound
  • E a polyphenol
  • the adhesive composition for organic fibers of the present invention comprises (A) a rubber latex having an unsaturated diene, (B) casein, and.
  • the organic fiber-rubber composite of the present invention is a composite of organic fibers and rubber, and is characterized in that the organic fibers are coated with the above-mentioned adhesive composition for organic fibers.
  • the tire of the present invention is characterized by using the above-mentioned organic fiber-rubber composite.
  • an adhesive composition for organic fibers an organic fiber-rubber, which can secure desired adhesiveness without using resorcin, is excellent in environmental friendliness, and does not impair workability during use. Complexes and tires can be provided.
  • FIG. 1 It is a schematic diagram which shows an example of the step of coating an organic fiber cord with an adhesive composition for organic fibers by a dipping process.
  • C-1 The present invention when a water-dispersible (heat-dissociable blocked) isocyanate compound composed of an addition product of a polyisocyanate having an aromatic ring and a blocking agent having one or more active hydrogen groups is used.
  • C-2 Heat Dissociative Blocked
  • the adhesive composition for organic fibers of the present invention comprises (A) a rubber latex having an unsaturated diene, (B) casein, and The following (C) to (E): (C) (Thermal dissociative blocked) Aqueous compound having an isocyanate group, (D) Epoxide compound and (E) It is characterized by containing one or more compounds selected from the group consisting of polyphenols and not containing resorcin.
  • the above configuration makes it possible to satisfactorily secure the adhesiveness between the organic fibers and the coated rubber composition without using resorcin.
  • it is selected from the group consisting of (A) a rubber latex having an unsaturated diene, (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group, (D) an epoxide compound and (E) a polyphenol.
  • the one or more compounds contribute to the improvement of the adhesiveness between the organic fiber and the coated rubber composition.
  • the adhesive composition for organic fibers of the present invention by using (B) casein, the adhesiveness of the rubber latex measured as the mechanical stability of the adhesive liquid under shear strain is suppressed. As a result, in the step of coating the organic fiber with the adhesive composition and drying and heat-curing it, it is possible to suppress the adhesion of the adhesive composition to the roll or the like, and the workability is improved. Further, according to the adhesive composition for organic fibers of the present invention, the environmental load can be reduced by not containing resorcin.
  • the adhesive composition of the present invention does not contain formaldehyde.
  • Organic fiber cord of an example of the organic fiber according to the adhesive composition for organic fiber of the present invention is used to supplement the strength of a rubber article such as a tire.
  • the organic fiber cord is used as a reinforcing material, first, the raw yarn of the spun organic fiber is twisted to obtain 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 prepare an organic fiber-rubber composite, and the organic fiber is produced.
  • the rubber composite can be used as a reinforcing member for rubber articles such as tires.
  • the material of the organic fiber is not particularly limited, but is limited to an aliphatic polyamide fiber such as polyester, 6-nylon, 6,6-nylon, and 4,6-nylon, a protein fiber such as an artificial fibroin fiber, a polyketone fiber, and a polynona.
  • aliphatic polyamide fiber such as polyester, 6-nylon, 6,6-nylon, and 4,6-nylon
  • a protein fiber such as an artificial fibroin fiber
  • a polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial fibroin fiber
  • polyketone fiber such as an artificial
  • 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 include glycols such as ethylene glycol, propylene glycol, butylene glycol, methoxypolyethylene glycol and pentaerythritol, and terephthalic acid, isophthalic acid and dimethyl forms thereof. Examples thereof include those obtained by condensation by an esterification reaction or a transesterification reaction with certain dicarboxylic acids.
  • 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 for the purpose of reinforcing rubber articles such as tires 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 rubber latex having (A) unsaturated diene in the adhesive composition for organic fibers of the present invention means a rubber latex containing unsaturated diene having vulcanizability by sulfur.
  • the rubber latex having (A) unsaturated diene contained in the adhesive composition for organic fibers will be described with reference to FIGS. 2 and 3. .
  • the rubber latex 11 having an unsaturated diene is a component for adhering the adhesive layer 32 of the adhesive composition 2 for organic fibers and the coated rubber composition 33 as an adherend thereof.
  • the rubber latex 11 having the unsaturated diene is compatible with the rubber polymer contained in the coated rubber composition 33 which is the adherend, and further, the unsaturated diene moiety is co-vulcanized to co-vulcanize the rubber. Form the bond 21.
  • the adhesive composition for organic fibers of the present invention containing a rubber latex having an unsaturated diene the organic fibers and the coated rubber composition can be satisfactorily adhered to each other.
  • the rubber latex having (A) unsaturated diene is not limited, but is limited to styrene-butadiene copolymer rubber latex, vinylpyridine-styrene-butadiene copolymer rubber latex, and carboxyl group-modified styrene-butadiene.
  • Synthetic rubber latex having unsaturated diene such as polymer rubber latex, nitrile rubber latex, and chloroprene rubber latex; natural rubber latex such as field latex, ammonia-treated latex, and deproteinized latex can be mentioned. These may be used alone or in combination of two or more.
  • 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 adhesive compositions for organic fibers and articles such as tires, and is used in the adhesive composition for organic fibers of the present invention. It also provides good bonding between the adhesive layer and the adherend rubber, and has the advantage of being relatively flexible and flexible, so that the adhesive layer does not split and the organic fibers are deformed. This is because it is possible to accompany it.
  • the content (solid content) of the rubber latex having (A) unsaturated diene in the total solid content in the adhesive composition for organic fibers of the present invention is not particularly limited. , 25% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more. Further, the content of the rubber latex having (A) unsaturated diene is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less. When the content of the rubber latex having (A) unsaturated diene 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 is more appropriate.
  • the adhered state of the coated rubber in the organic fiber-rubber composite becomes more excellent.
  • the content of the rubber latex having (A) unsaturated diene is 95% by mass or less, the amount of the resin component contained as another component in the adhesive composition is relatively constant or higher. This is because it can be secured, and as a result, the coagulation-breaking resistance of the adhesive layer is sufficiently secured, and the breakage in the adhesive layer is less likely to occur, so that sufficient adhesiveness can be obtained. be.
  • the rubber latex having (A) unsaturated diene for example, after dissolving an emulsifier such as potassium loginate in water, a mixture of monomers is added thereto, and an electrolyte such as sodium phosphate and an electrolyte such as sodium phosphate and the like are further added.
  • an emulsifier such as potassium loginate
  • an electrolyte such as sodium phosphate and an electrolyte such as sodium phosphate and the like
  • Peroxides and the like are added as a polymerization initiator to carry out polymerization, and after reaching a predetermined conversion rate, a charge transfer agent is added to terminate the polymerization, and further, residual monomers are removed. Can be obtained by It is also preferable to use a chain transfer agent during the polymerization.
  • 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 ,
  • 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 ,
  • nonionic surfactants such as alkyl ester type, alkyl ether type and alkyl phenyl ether type of polyethylene glycol are used.
  • a metal salt of logonic acid particularly an alkali metal salt of logonic acid
  • Rosinic acid is a mixture of resin acids having a similar chemical structure, mainly composed of tricyclic diterpenes obtained from pine fat 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 usually 0.1 to 8 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of all the monomers 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. Above all, it is preferable to use potassium persulfate.
  • 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.
  • -Bifunctional mercaptans such as decandithiols and ethylene glycol dithioglycolates; Trifunctional mercaptans such as canditrithiols and trimethylolpropanetristhioglycolates; Mercaptans; 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. Above all, it is preferable to use t-dodecyl mercaptan.
  • the amount of such a chain transfer agent used is usually 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 used in the latex polymerization. ..
  • the latex includes antiaging agents such as hindered phenols, silicone-based, higher alcohol-based, mineral oil-based defoaming agents, reaction terminators, and antifreeze agents, if necessary.
  • antiaging agents such as hindered phenols, silicone-based, higher alcohol-based, mineral oil-based defoaming agents, reaction terminators, and antifreeze agents, if necessary.
  • General-purpose additives such as may be used.
  • the vinylpyridine-styrene-butadiene copolymer rubber latex is a ternary copolymer of a vinylpyridine-based monomer, a styrene-based monomer, and a conjugated diene-based butadiene monomer. These monomers may further contain other copolymerizable monomers.
  • the vinyl pyridine-based monomer includes vinyl pyridine and substituted vinyl pyridine in which a hydrogen atom in the vinyl pyridine is substituted with a substituent.
  • vinylpyridine-based monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine and the like. Of these, 2-vinylpyridine is preferable.
  • 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 vinyl pyridine-styrene-butadiene copolymer rubber latex, and specifically, for example, described in JP-A-9-78045 according to the study by the present inventors. Method can be used. Then, by utilizing these methods, it is possible to have 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. can.
  • the vinyl pyridine-styrene-butadiene copolymer rubber latex as commercially available products of the copolymer having a monomer mixture ratio having a uniform composition in the same particles, Nippon A & L Inc.'s Nipol 2518 and Nippon A & L Inc. Examples thereof include polymer made by Co., Ltd. Examples of commercially available copolymers having different composition ratios within the same particle include V0658 manufactured by JSR Corporation. All of these can be used as the rubber latex having (A) unsaturated diene in the adhesive composition for organic fibers 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 20% by mass. If the following 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 used. This is because it also leads to ensuring the adhesive strength while making the co-sulfurization property of the above appropriate.
  • the composition ratio of the vinyl pyridine: styrene: butadiene monomer mixture can be preferably, for example, 15:15:70.
  • casein (B) in the adhesive composition for organic fibers of the present invention a commercially available casein can be used, and it is particularly limited as long as the adhesive composition for organic fibers of the present invention can be obtained. Not done.
  • casein examples include acid casein, specifically, casein hydrochloride, casein sulfate, rennet casein, lactic casein, or modified compounds thereof.
  • Casein may be casein salt.
  • Casein salt is a product obtained by treating acid casein with a neutralizing agent and drying it, and examples thereof include casein sodium, casein potassium, casein calcium and casein salt mixture depending on the neutralizing agent used. ..
  • the above-mentioned (B) casein is a phosphoprotein contained in a large amount in milk.
  • the casein is an extract of a phosphoprotein that normally exists as casein micelles and is contained in milk.
  • the method for extracting phosphoprotein from milk include a method of coagulating and extracting from whey by adding an acid (acid casein), a method of concentrating casein micelles by a membrane separation technique (Milk Protein Concentrate), and the like.
  • the phosphoprotein acid casein obtained by the addition of acid has an appropriate viscosity and is used in a natural adhesive composition known as casein glue. By using this acid casein, it is coated with organic fibers. Adhesiveness to the rubber composition is improved.
  • casein or casein salts used in the present invention are available in solid form such as powder, paste form, solution, dispersion or suspension in aqueous form, but to the adhesive composition of the present invention. In the use of, it is preferable to use it in the state of a solution, particularly as an aqueous solution.
  • Adhesion between organic fibers and coated rubber compositions by using as the casein an isoelectrically precipitated casein derived from milk or an alkaline salt thereof in the form of a solid, a paste, a solution, a dispersion or a suspension. However, it becomes better.
  • caseins 12 form a network in water below the gelation temperature to cover the surface of the rubber latex 11 (core) having an unsaturated diene.
  • the rubber latex 11 having an unsaturated diene is negatively (-) charged due to the carboxylic acid of the rosinate emulsified on the surface, and contains the amino group (-NH 2 ) of 12 molecules of casein and the case where it is contained.
  • a cationic group such as a thiol group (-SH) is adsorbed by an electrostatic attraction to form a complex, and this coating suppresses the adhesiveness of the rubber latex 11 having an unsaturated diene ().
  • Latex-casein protective film effect 20 (see Figure 2).
  • the adhesive composition for organic fibers of the present invention containing (B) casein suppresses the adhesiveness of the rubber latex measured as an index of the mechanical stability of the adhesive liquid under shear strain. This makes it possible to suppress the adhesion of the organic fiber adhesive composition to a roll or the like in the step of coating the organic fiber cord with the organic fiber adhesive composition and drying / thermosetting the organic fiber cord, resulting in good workability. It will be something like that.
  • casein 12 in the adhesive composition 2 for organic fibers of the present invention coated on the surface of the organic fiber cord 1 is chemically bonded to the carboxylic acid portion of loginic acid having high reactivity by heat treatment by an amide bond or an ester bond.
  • the adhesiveness between the organic fiber and the coated rubber composition becomes good.
  • the adhesive composition for organic fibers of the present invention contains (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group
  • casein 12 has an amino group (-NH 2 ) and a hydroxyl group (-NH 2).
  • -OH) or the like forms a casein-isocyanate crosslink 22 with the activated isocyanate group 14 of the urethane resin 13 formed of the aqueous compound having a (heat dissociable blocked) isocyanate group by high temperature heat treatment after drying. (See FIG. 3).
  • the adhesive composition containing (B) casein and (C) an aqueous compound having a (heat dissociative blocked) isocyanate group has better adhesiveness between the organic fiber and the coated rubber composition. Become.
  • casein 12 is a phosphoprotein, it has a characteristic of forming casein micelles via the phosphate group of casein (B). ) Since the caseins interact with each other such as being strongly crosslinked, the adhesiveness between the organic fiber and the coated rubber composition becomes better.
  • acid casein Since acid casein does not dissolve just by mixing with water, it dissolves when alkaline substances (sodium hydroxide, borax, ammonia, etc.) are added and stirred. In addition, it dissolves quickly when it is stirred while applying heat. Casein is said to be a protein that is not easily denatured by heat, and denaturation begins at around 80 ° C, so the temperature is preferably 80 ° C or lower. Acid casein exerts the function of suppressing latex adhesion in the present invention because the component dissolved in water has the above-mentioned latex-casein protective film effect 20 even in a liquid suspended with water, but the suspended particles of casein that do not dissolve. If there is, the workability is deteriorated due to the adhesion of particles to the apparatus, so it is preferable to use it in a completely water-soluble liquid state.
  • alkaline substances sodium hydroxide, borax, ammonia, etc.
  • the milk protein component in milk consists of milk syrup and casein, and casein exists in the form of a calcium-casein-phosphate complex together with the component phosphate in milk.
  • This casein can be separated from whey by adjusting skim milk to pH 4.6 and precipitating it.
  • This casein micelle is separated from whey in milk by redissolving acid casein, which is isoelectrically precipitated with acid, with alkali, and is used as a functional protein material produced at the industrial level, not only for foods but also for pharmaceuticals. , Widely used in the manufacture of cosmetics.
  • milk materials such as Milk Protein Concentrate (MPC), which is obtained by membrane-separating and concentrating casein micelles in milk, have a relatively high unit price as compared with acid casein, but can be used as casein.
  • MPC Milk Protein Concentrate
  • an aqueous solution obtained by adding phosphate ions, calcium ions, etc., which form casein micelles in milk, to acid casein or a salt thereof can be used.
  • the cross-linking between casein molecules by the calcium-phosphoric acid complex is strengthened, the destructive resistance of the adhesive layer made of the adhesive composition is improved, which may improve the adhesive force. Therefore, the adhesive composition of the present invention may be improved.
  • the content (solid content) of casein (B) in the total solid content in the adhesive composition for organic fibers of the present invention is not particularly limited, but is 0.1% by mass or more. It is preferably 0.5% by mass or more, more preferably 0.8% by mass or more.
  • the content of (B) casein is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • the content of the casein (B) is 0.1% by mass or more, it is possible to further suppress the adhesion of the adhesive composition for organic fibers to a roll or the like, and the workability is improved. Because there are advantages. Further, when the content of (B) casein is 15% by mass or less, the amount of casein contained in the adhesive layer does not become too large, and the destructive drag of the adhesive layer can be sufficiently secured. Is.
  • the adhesive composition for organic fibers of the present invention is one selected from the group consisting of (C) an aqueous compound having a (heat dissociative blocked) isocyanate group, (D) an epoxide compound, and (E) a polyphenol. Contains the above compounds.
  • (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group and (D) an epoxide compound function as a cross-linking agent to form an organic fiber and a coated rubber. Contributes to improving the adhesiveness with the composition.
  • (E) polyphenol has a function of improving the affinity between the adhesive composition and the surface of the organic fiber, and as a result, the adhesiveness between the organic fiber and the coated rubber composition can be improved.
  • the (heat dissociative blocked) isocyanate group of the aqueous compound having the (heat dissociative blocked) isocyanate group in (C) means a heat dissociative blocked isocyanate group or an isocyanate group.
  • the above-mentioned (heat-dissociable blocked) isocyanate group is (a) a heat-dissociable blocked isocyanate group generated by reacting an isocyanate group with a heat-dissociable blocking agent for the isocyanate group, (b).
  • the aqueous solution of the aqueous compound having an isocyanate group (C) indicates that it is water-soluble or water-dispersible. Further, the above-mentioned water-soluble does not necessarily mean completely water-soluble, but also means that it is partially water-soluble or that phase separation does not occur in the aqueous solution of the adhesive composition for organic fibers. do.
  • the aqueous compound having (C) (thermally dissociable blocked) isocyanate group is water-dispersed consisting of (C-1) an addition product of a polyisocyanate having an aromatic ring and a blocking agent having one or more active hydrogen groups. It is preferably a sex (heat dissociable blocked) isocyanate compound (hereinafter, also simply referred to as “(C-1) component”). In this case, the adhesiveness between the organic fiber and the coated rubber composition becomes better.
  • the active hydrogen group includes hydrogen that becomes active hydrogen (atomic hydrogen (hydrogen radical) and hydride ion (hydride)) when placed under suitable conditions. It means the radical.
  • the active hydrogen group include an amino group and a hydroxyl group.
  • the heat-dissociable blocking agent is a blocking agent compound capable of restoring the isocyanate group by dissociating the blocking agent by heat treatment as necessary while protecting the isocyanate group from an arbitrary chemical reaction. If there is, it is not particularly limited. Specifically, in the step shown in FIG. 1, at the temperature of the heat treatment for thermosetting after the adhesive treatment liquid was adhered and dried, the reaction was suppressed by being sealed with a heat dissociable blocking agent. It is preferable that the thermal dissociation temperature is such that the crosslinking reactivity of the isocyanate group can be restored.
  • the blocking agent examples include alcohol, phenol, active methylene, oxime, lactam, amine and the like, and are not particularly limited, and specifically, lactams such as ⁇ -caprolactam, ⁇ -valerolactam and ⁇ -butyrolactam; , Cresol, ethylphenol, butylphenol, octylphenol, nonylphenol, dinonylphenol, thiophenol, chlorphenol, amylphenol and other phenols; Alcohols such as butanol, isopropyl alcohol, butyl alcohol, cyclohexanol; malonic acid dialkyl esters such as dimethyl malonate and diethyl malonate; active methylene such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, butyl mercaptan, dodecyl mercaptan Mercaptans such as; amides such as acetanilide and acetate amide;
  • phenol, ⁇ -caprolactam and ketooxime which can be easily obtained by stably heat-curing the adhesive composition by thermal dissociation by heating, can be preferably used.
  • the component (C-1) specifically contains aromatic polyisocyanates or aromatic aliphatic polyisocyanates, and examples of the aromatic isocyanates include phenylene such as m-phenylenediocyanate and p-phenylenedi isocyanate.
  • Diisocyanates Diisocyanates; Tolylene diisocyanates such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI); 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), dialkyldiphenylmethane diisocyanate , Tetraalkyldiphenylmethane diisocyanates and other diphenylmethane diisocyanates; polymethylene polyphenyl polyisocyanate (polymeric MDI); m- or p-isocyanatophenylsulfonyl isocyanates; 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl -4,4'-Diisocyanatobiphenyls such as diisocyanatobiphenyl; Naphthalene diisocyanates such as 1,5-naphthylene diisocyan
  • 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 polyisocyanate can be mentioned.
  • aromatic isocyanates are preferable, and more preferably diphenylmethane diisocyanates (MDIs) or polys, from the viewpoint of the code focusing property of the adhesive composition.
  • Methylene polyphenyl polyisocyanate polymeric MDI
  • MDI diphenylmethane diisocyanate
  • a block body of methylene diphenyl isocyanates particularly a block body of methylene diphenyl diisocyanate (diphenylmethane diisocyanate) as the component (C-1)
  • the adhesiveness between the organic fiber and the coated rubber composition becomes better.
  • the aqueous compound having the (C) (heat dissociative blocked) isocyanate group is the aqueous urethane compound having the (C-2) (heat dissociative blocked) isocyanate group (hereinafter, simply "(C-2)). It is more preferable that it is also referred to as "component”). In this case as well, the adhesiveness between the organic fiber and the coated rubber composition becomes better.
  • component hereinafter, simply “component”
  • the content (solid content) of the aqueous compound having the (heat dissociable blocked) isocyanate group described above (C) in the total solid content of the adhesive composition for organic fibers of the present invention is particularly limited. Although it is not, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more.
  • the content of the aqueous compound having the (C) (heat dissociative blocked) isocyanate group is preferably 75% by mass or less, more preferably 60% by mass or less, and 45% by mass or less. It is more preferable to have.
  • the aqueous solution having the (C) (heat dissociable blocked) isocyanate group instead of the phenolic resin in which resorcin and formaldehyde are co-condensed.
  • the compound acts as an adhesion promoter with the following two functional effects (a) and (b).
  • the above-mentioned (C) (heat dissociative blocked) aqueous compound having an isocyanate group contributes to the feature that the adhesiveness between the organic fiber and the coated rubber composition is good. do.
  • B In the adhesive layer of the adhesive composition for organic fibers, a three-dimensional network structure is formed by cross-linking with the isocyanate group by the compound having the (heat dissociable blocked) isocyanate group to reinforce the adhesive layer.
  • the functional effects (a) and (b) of the aqueous compound having the above (C) (heat dissociative blocked) isocyanate group as the above two adhesion promoters will be described in detail below.
  • the aqueous compound having the (C) (heat dissociative blocked) isocyanate group is the component (C-1)
  • the above (C) (heat) is also referred to with reference to FIG.
  • the case where the aqueous compound having a dissociative blocked) isocyanate group is the component (C-2) will be described with reference to FIG.
  • 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 aromatic ring or 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, in the organic fiber adhesive composition used for the organic fiber cord made of polyester, in order to obtain sufficient adhesive strength, the organic fiber adhesive composition is a polymer chain of an organic fiber.
  • An aromatic ring having aromatic ⁇ electrons is provided for the purpose of dispersing in the gaps of the organic fibers and ensuring that the adhesive layer of the organic fiber adhesive composition adheres to the surface of the polymer chain of the organic fibers.
  • Molecules having a planar structure (a portion that easily diffuses into organic fibers) having a side surface have been contained as an adhesion promoter.
  • the above component (C-1) has been conventionally used.
  • the component (C-1) is preferably (blocked) isocyanate (see Patent Document 3) such as methylene diphenyl diisocyanate having a particle size of 0.01 to 0.50 ⁇ m.
  • the component (C-1) 40 is an organic fiber cord in the adhesive layer 32 according to the adhesive composition 2 for organic fibers.
  • the adhesive composition 2 for organic fibers is organic by forming a casein-isocyanate bridge 22 by a covalent bond with the casein 12 contained in the adhesive layer while diffusing into 1 (aromatic isocyanate-organic fiber diffusion effect 41).
  • the adhesive layer 32 of the adhesive composition 2 for organic fibers is dispersed in the gaps between the polymer chains of the fiber cord 1, and the adhesive layer 32 is in close contact with the surface of the polymer chains of the organic fiber cord 1.
  • the particle size of the component (C-1) is preferably 0.01 to 0.50 ⁇ m as described above.
  • the component (C-1) is aromatic from the surface of the polymer chain of the organic fiber in the adhesive layer over time. It has the property of easily diffusing into the gaps between the polymer chains of organic fibers in which more abundant sex ⁇ electrons are present, and the effect as an adhesion promoter is reduced accordingly. Therefore, in order to remain on the surface of the organic fiber, it is necessary that the particle size of the component (C-1) is large to some extent.
  • the particle size of the component (C-1) is 0.50 ⁇ m or less, the smaller the particle size, the more difficult it is for the component (C-1) to settle in the liquid, and the dispersion in the adhesive layer is non-uniform. This is because it is difficult to become.
  • the hydrophilic portion which is a portion which is difficult to diffuse into the organic fiber. It is more preferable to contain an aqueous urethane compound having a (C-2) (thermally dissociable blocked) isocyanate group, which also has a molecular chain portion of the above.
  • the urethane resin 13 formed by the component (C-2) in the adhesive layer 32 of the organic fiber adhesive composition 2 can easily obtain an interaction with the organic fiber cord 1. It has both a portion 15 and a portion 16 that is difficult to diffuse into the organic fiber cord 1.
  • the presence of the portion 15 that easily interacts with the organic fiber cord ensures that the adhesive layer 32 of the organic fiber adhesive composition 2 adheres to the surface of the polymer chain of the organic fiber cord 1.
  • the urethane resin 13 formed by the component (C-2) has a long-lasting functional effect of promoting adhesiveness at the interface with the adhesive layer 32. (Aqueous urethane-organic fiber interface effect 24).
  • the adhesive composition for organic fibers containing the above component (C-2) has good adhesiveness between the organic fiber cord and the coated rubber composition.
  • the aqueous compound having the (heat dissociable blocked) isocyanate group in (C) is an aromatic polyisocyanate compound having an anionic or nonionic water-soluble functional group, and the hydrophobic organic fiber code 1 Since it tends to disperse in water from the surface, the above component (C-2) is more preferable.
  • the compound does not settle in the liquid and disperse in the adhesive layer becomes non-uniform and does not aggregate.
  • the dipping bath (dipping tank) 3 of FIG. 1 is stirred.
  • the above component (C-2) is contained as an adhesion promoter. Since the component (C-2) contains an alkylene oxide portion or the like in its molecule, it can be uniformly dispersed in water by self-emulsification due to swelling of water or the like.
  • the component (C-2) uniformly dispersed in water contains a hydrophobic organic isocyanate moiety in its molecule, it is adjacent to each other in the same manner as the water-soluble urethane used in, for example, an associative thickener.
  • the hydrophobic parts of the water-soluble urethane form stable associative micelles, and have a three-dimensional network structure due to the hydrophobic interaction between the aqueous urethanes uniformly dispersed in the liquid.
  • the adhesive composition for organic fibers having the above-mentioned hydrophobic bond having a three-dimensional network structure is coated on the organic fibers, and then dried and thermoset. Then, as shown in FIG. 3, the activated isocyanate groups 14 in which the blocking agent is thermally dissociated form the activated isocyanate crosslinks 23 by covalent bonds between the adjacent ones, and are formed by the above component (C-2).
  • An adhesive layer containing a three-dimensional network structure of the urethane resin 13 can be obtained.
  • the adhesive composition for organic fibers containing the component (C-2) the adhesiveness between the organic fibers and the coated rubber composition is good.
  • the heat-dissociating blocking agent of the component (C-2) can dissociate the blocking agent by heat treatment as necessary while protecting the isocyanate group from any chemical reaction to restore the isocyanate group.
  • the blocking agent compound is not particularly limited as long as it is possible.
  • the same compound as the blocking agent described above can be used for the component (C-1), and phenol, thiophenol, chlorphenol, cresol, resorcinol, p- Phenols such as sec-butylphenol, p-tert-butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol; secondary or tertiary alcohols such as isopropyl alcohol, tert-butyl alcohol; diphenylamine, Aromatic secondary amines such as xylidine; phthalic acidimides; lactams such as ⁇ -valerolactam; caprolactams such as ⁇ -caprolactam; malonic acid dialkyl esters such as diethyl malonate and dimethyl malonate, acetylacetone, aceto Active methylene compounds such as acetic acid alkyl esters; oximes such as
  • phenol, ⁇ -caprolactam and ketooxime which can be easily obtained by stably heat-curing the adhesive composition by thermal dissociation by heating, can be preferably used.
  • the aqueous solution of the aqueous urethane compound means that it is water-soluble or water-dispersible. Further, the above-mentioned water-soluble does not necessarily mean completely water-soluble, but also means that it is partially water-soluble or that phase separation does not occur in the aqueous solution of the adhesive composition for organic fibers. do.
  • the urethane compound of the aqueous urethane compound is a compound having a covalent bond formed between nitrogen of an amine and carbon of a carbonyl group, and means a compound represented by the following general formula (2).
  • R and R' represent a hydrocarbon group.
  • the molecular weight of the aqueous urethane compound having the (C-2) (heat dissociative blocked) isocyanate group is not particularly limited as long as it can maintain aqueous properties, and 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 above component (C-2) is not particularly limited, and a known method such as the method described in JP-A-63-51474 can be used.
  • a preferred embodiment of the component (C-2) 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, and ( ⁇ ) 2 or more and 4 Anionic, cationic or nonionic with a compound having no more than 5,000 active hydrogen groups and a number average molecular weight of 5,000 or less, ( ⁇ ) a thermally dissociable blocking agent, and ( ⁇ ) at least one active hydrogen group.
  • the composition ratio of the (thermally dissociable blocked) isocyanate group in the above reaction product is 0.5% by mass or more and 11% by mass or less. In this case, the adhesiveness between the organic fiber and the coated rubber composition becomes better. Since such a component (C-2) has both a moiety composed of a (heat dissociative blocked) isocyanate group and a hydrophilic moiety having a hydrophilic group, it has an advantage that the self-water solubility of the urethane compound is enhanced. Because.
  • the mixing ratios of ( ⁇ ), ( ⁇ ), ( ⁇ ) and ( ⁇ ) to the total amount were 40% by mass or more and 85% by mass or less for ( ⁇ ), and 5% by mass for ( ⁇ ). As mentioned above, 35% by mass or less, ( ⁇ ) is 5% by mass or more and 35% by mass or less, and ( ⁇ ) is 5% by mass or more and 35% by mass or less.
  • the organic polyisocyanate compound having a number average molecular weight of 2,000 or less having ( ⁇ ) 3 or more and 5 or less functional groups is not particularly limited, but is an aromatic polyisocyanate compound and an oligomer thereof. Is preferable, and other aliphatic, alicyclic, or heterocyclic polyisocyanate compounds and oligomers thereof may be used.
  • the component (C-2), which is a 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 organic. This is because it becomes easier to disperse in the gaps between the polymer chains of the fiber.
  • 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, Examples thereof include 4-diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-
  • heterocyclic polyisocyanate compound examples include a tolylene diisocyanate adduct of 1,3,5-tris (2'-hydroxyethyl) isocyanuric acid, and examples of the aromatic polyisocyanate compound include m-phenylenediocyanate.
  • p-phenylenedi isocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m -Tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, methintris (4-phenylisocyanate), tris (4-isocyanatophenyl) methane, tris thiophosphate (4-isocyanatophenyl ester), 3-isopropenyl- Examples thereof include ⁇ ', ⁇ '-dimethylbenzyl isocyanate and a mixture thereof, or modified products of these polyisocyanate compounds such as carbodiimide, polyol and allophanate.
  • 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 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, from (i) to (vii) below. ) And the like selected from the group consisting of.
  • C2-C4 alkylene oxide heavy adducts of polyhydric amines, polyhydric phenols and amino alcohols C2-C4 alkylene oxide heavy adducts of C3 and higher polyhydric alcohols, C2-C4 alkylene oxide copolymers, Alternatively, an alkylene oxide polymer of C3 to C4.
  • the active hydrogen group includes hydrogen that becomes active hydrogen (atomic hydrogen (hydrogen radical) and hydride ion (hydride)) when placed under suitable conditions.
  • the active hydrogen group include an amino group and a hydroxyl group.
  • At least one active hydrogen group and at least one anionic hydrophilic group of a compound having at least one active hydrogen group and at least one anionic, cationic or nonionic hydrophilic group are not particularly limited, and examples thereof include aminosulfonic acids such as taurine, N-methyltaurin, N-butyltaurin and sulfanic acid, and aminocarboxylic acids such as glycine and alanine.
  • the method for synthesizing the component (C-2) by mixing and reacting the above ( ⁇ ), ( ⁇ ), ( ⁇ ) and ( ⁇ ) is not particularly limited, but is not particularly limited.
  • a known method such as the method described in Japanese Patent Application Laid-Open No. 63-51474 can be used.
  • C-2 (Thermal Dissociative Blocked) Another Preferred Embodiment of an Aqueous Urethane Compound Having an Isocyanate Group
  • Another preferred embodiment of the component (C-2) 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, and ( ⁇ ) 2 or more.
  • a compound having one hydrophilic group and a compound other than ( ⁇ ), ( ⁇ ), ( ⁇ ) and ( ⁇ ) containing a ( ⁇ ) active hydrogen group are mixed so as to have a predetermined mixing ratio.
  • the composition of the (thermally dissociable blocked) isocyanate group in the above reaction product when the reaction product is mixed and reacted and the molecular weight of the isocyanate group (-NCO) is 42.
  • the ratio is 0.5% by mass or more and 11% by mass or less. Since such a component (C-2) has both a moiety composed of a (heat dissociative blocked) isocyanate group and a hydrophilic moiety having a hydrophilic group, it has an advantage that the self-water solubility of the urethane compound is enhanced. Because.
  • the mixing ratios of ( ⁇ ), ( ⁇ ), ( ⁇ ), ( ⁇ ) and ( ⁇ ) to the total amount are 40% by mass or more for ( ⁇ ), less than 85% by mass, and ( ⁇ ). 5% by mass or more, 35% by mass or less, 5% by mass or more for ( ⁇ ), 35% by mass or less, 5% by mass or more for ( ⁇ ), 35% by mass or less, 0 for ( ⁇ ) More than mass% and less than 45% by mass.
  • the method for synthesizing the component (C-2) by mixing and reacting the above ( ⁇ ), ( ⁇ ), ( ⁇ ), ( ⁇ ) and ( ⁇ ) is not particularly limited. , A known method such as the method described in JP-A-63-51474.
  • C-2 (Thermal Dissociative Blocked) Yet Another Preferred Embodiment of an Aqueous Urethane Compound Having an Isocyanate Group
  • C-2 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 an 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 or hydrophilic polyether chain that produces at least one salt, from which the active hydrogen group has been eliminated.
  • n is an integer of 2 or more and 4 or less
  • p + m is an integer of 2 or more and 4 or less (m ⁇ 0.25) It is characterized by being represented by].
  • the adhesiveness between the organic fiber and the coated rubber composition becomes better.
  • the component (C-2) has an advantage that the self-water solubility of the urethane compound is enhanced because it has both a moiety composed of a (heat dissociative blocked) isocyanate group and a hydrophilic moiety having a hydrophilic group. be.
  • the organic polyisocyanate compound which is the residue from which the active hydrogen group of the organic polyisocyanate compound has been eliminated, which is A in the general formula (1), contains an aromatic ring. This is because the component (C-2) is more easily dispersed in the gaps between the polymer chains of the organic fiber.
  • 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.
  • the polyol compound having a number of hydroxyl groups of 5,000 or less and having a number average molecular weight of 5,000 or less is not particularly limited, but specifically, a compound selected from the group consisting of the following (i) to (vi) and the like. Can be mentioned.
  • Polyester polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
  • the above component (C-2) is not particularly limited, but commercially available products such as Elastron BN27, BN77, and BN11 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. can also be used. Among them, Elastron BN77 is preferable.
  • One embodiment of the adhesive composition for organic fibers of the present invention comprises (A) a rubber latex having an unsaturated diene, (B) casein, and (D) an epoxide compound.
  • This adhesive composition does not contain resorcin.
  • epoxide compound means a compound having oxacyclopropane (oxylan) (epoxy group), which is a 3-membered ring ether, in its structural formula.
  • the epoxide compound (D) functions as a cross-linking agent component in the adhesive composition for organic fibers. That is, when the adhesive composition contains (D) an epoxide compound, cross-linking is introduced between the hydroxyl group and the amine group contained in the amino acid unit of (B) casein, and the breaking resistance of the adhesive layer is improved. Significant performance improvements will be seen in the adhesive strength at high temperatures.
  • the (D) epoxide compound is mixed with the above-mentioned (C) (thermally dissociative blocked) aqueous compound having an isocyanate group and heated.
  • the above-mentioned adhesive composition for organic fibers mainly composed of urethane bonds is obtained.
  • the epoxide group of the (D) epoxide compound and the amine, alcohol, thiol, phenol, carboxylic acid, or (the heat dissociable block dissociated) of the aqueous compound having the (C) (heat dissociable blocked) isocyanate group is because cross-linking due to a nucleophilic reaction with isocyanate or the like is added, and creep and flow due to stress in a high temperature region are suppressed.
  • the epoxy group of the above (D) epoxide compound is polyfunctional. This is because the effect of the suppression is enhanced, the destructive drag of the adhesive layer by the adhesive composition for organic fibers is further enhanced, and the adhesive strength at a high temperature is also enhanced.
  • the above (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, so that in the adhesive composition for organic fibers, creep and flow due to stress in a high temperature region are further suppressed, the rupture resistance of the adhesive layer is further enhanced, and the high temperature is obtained. This is because the adhesive strength in the epoxide is also higher.
  • the (D) epoxide compound examples include, for example, diethylene glycol / diglycidyl ether, polyethylene glycol / diglycidyl ether, polypropylene glycol / diglycidyl ether, neopentyl glycol / diglycidyl ether, and 1,6-hexanediol di.
  • Polyhydric alcohols such as glycidyl ether, glycerol / polyglycidyl ether, trimethylolpropane / polyglycidyl ether, polyglycerol / polyglycidyl ether, pentaerythiol / polyglycidyl ether, diglycerol / polyglycidyl ether, sorbitol / polyglycidyl ether, etc.
  • a reaction product of a polyhydric alcohol and epichlorohydrin, or a novolak type epoxy resin is preferable.
  • the epoxide compound (D) when it is a reaction product of polyhydric alcohols and epichlorohydrin, it can be dissolved in water or dispersed in water by emulsification and used, so that its production is easier. ,preferable.
  • Commercially available chemicals can be used for the sorbitol / polyglycidyl ether, polyglycerol / polyglycidyl ether, and novolak type epoxy resin.
  • the above (D) epoxide compound can be used by dissolving it in water or dispersing it in water by emulsification.
  • the above (D) epoxide compound can be dissolved in water as it is.
  • the above (D) epoxide compound is dissolved in a small amount of solvent as needed, and the solution is used with known emulsifiers such as sodium alkylbenzene sulfonic acid, sodium dioctylsulfosuccinate salt, nonylphenolethylene oxide adduct and the like. It can be used to make an emulsified solution by emulsifying it in water.
  • the content (solid content content) of the epoxide compound (D) in the total solid content of the adhesive composition for organic fibers of the present invention is not particularly limited, but is 0.1% by mass or more. It is preferably present, and more preferably 5% by mass or more.
  • the content (solid content content) of the (D) epoxide compound is preferably 40% by mass or less, more preferably 25% 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, when the content 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 adhered rubber and the adherend rubber can be secured. This is because the adhesiveness of the material becomes better.
  • One embodiment of the adhesive composition for organic fibers of the present invention comprises (A) a rubber latex having an unsaturated diene, (B) casein, and (E) a polyphenol.
  • This adhesive composition does not contain resorcin. Moreover, it is preferable that this adhesive composition does not contain formaldehyde.
  • the above (E) polyphenol is preferably a plant-derived compound having a plurality of phenolic hydroxy groups in the molecule. In this case, the adhesiveness between the organic fiber and the coated rubber composition becomes better.
  • the above (E) polyphenol is preferably lignin or a derivative thereof.
  • the adhesiveness between the organic fiber and the coated rubber composition becomes better.
  • Lignin together with polysaccharides such as cellulose, is a major component of the plant cell wall of plants. Lignins contain, for example, functional groups such as hydroxyl groups, methoxy groups, carbonyl groups and carboxyl groups, but in particular, phenolic hydroxy groups are highly reactive and thus interact with cationic polymers such as casein. Can have an effect.
  • Lignin is a polymer with a structure based on phenylpropane, but since the molecular structure of lignin is various and it is a huge biopolymer forming a three-dimensional network structure, its molecular structure is still completely complete. It has not been clarified.
  • lignin Since natural lignin strongly forms a composite material together with polysaccharides such as cellulose in the plant cell wall, it is very difficult to isolate natural lignin without modification of the chemical structure.
  • Various industrial separation methods have been used to extract lignin from materials such as wood. Examples of the lignin obtained after separation include sulfonic acid lignin, kraft lignin, soda lignin, steam-blasted lignin and the like.
  • These industrially treated lignins from the viewpoint of availability and economy, are lignins that can be obtained on a larger scale than the pulp waste liquid of chemical pulping in the pulp and paper manufacturing process, that is, lignosulfonates or kraft lignins. Is a well-known material.
  • lignins examples include hydroxymethylated, epoxidized, denitrified, acylated or hydroxylated lignins, diethanolamine-modified lignins, enzyme-modified lignins, lacquerze-modified lignins, urea-modified lignins, lignosulfonates. , Arcel method lignin, alkaline granite method lignin, polyethylene glycol-added lignin, and the like.
  • the above-mentioned craft lignin is produced by putting wood chips such as hardwood, conifer, miscellaneous wood, bamboo, kenaf, and bagus as raw wood into a cooking pot together with a cooking liquid containing sodium hydroxide / sodium sulfide. It is a lignin derived from a chemical pulping method (high temperature and high pressure reaction) called the kraft cooking method, which is a high pressure reaction. It is obtained by adding acid and / or carbon dioxide to the kraft waste liquid obtained after kraft cooking to precipitate the dissolved lignin denaturant, and dehydrating and washing the produced precipitate.
  • Precipitation after dehydration / washing is purified by adding an organic solvent such as alcohol or acetone to separate impurities that are insoluble substances and drying them, or by introducing various functional groups as necessary. It can be performed.
  • an organic solvent such as alcohol or acetone
  • the above-mentioned craft lignin can be obtained and used as a commercially available product.
  • the lignin sulfonate is a lignin obtained from a waste liquid or the like eluted from sulfite pulp in a chemical pulping method by a sulfite cooking method in which wood chips are reacted at high temperature and high pressure together with a cooking solution using sulfite and / or sulfite.
  • Sulphonic acid and salts thereof with particular preference given to calcium lignin sulfonate, sodium lignin sulfonate, potassium lignin sulfonate, magnesium lignin sulfonate. Of these, sodium lignin sulfonate and the like are preferable.
  • These lignin sulfonates are available as commercial products. For example, as the lignin sulfonate or the modified lignin sulfonate, the Sun Extract series manufactured by Nippon Paper Industries, Ltd. can be used.
  • High-value-added products of lignin sulfonate include, for example, high-purity products, as well as lignin sulfonate heated in an alkaline aqueous solution using sodium hydroxide or ammonia in the presence of an oxidizing agent such as oxygen.
  • examples thereof include partially de-(low) sulfonated lignin sulfonate having a reduced degree of sulfonate.
  • the high-purity lignin sulfonate or modified lignin sulfonate the Pearllex series manufactured by Nippon Paper Industries, Ltd.
  • the Vanillex series manufactured by Nippon Paper Industries, Ltd. can be used. .. Among them, a partially de-(low) sulfonated lignin sulfonate having a reduced degree of sulfonate, manufactured by Tokyo Kasei Kogyo Co., Ltd., reagent name "lignin (alkali)" (CAS Number: 8061-51-6, solid powder). Body) is preferred.
  • the content (solid content content) of the above (E) polyphenol in the total solid content of the adhesive composition for organic fibers of the present invention is not particularly limited, but is 2% by mass or more. Is more preferable, 5% by mass or more is more preferable, and 7% by mass or more is further preferable.
  • the content of the polyphenol (E) is preferably 75% by mass or less, more preferably 50% by mass or less, and further preferably 35% by mass or less. This is because when the content of the polyphenol (E) is 2% by mass or more, the adhesiveness between the organic fiber and the coated rubber composition becomes better.
  • the amount of other components such as rubber latex to be blended in the adhesive composition for organic fibers can be relatively secured to a certain level or more. This is possible, and as a result, the adhesiveness with the adherend rubber becomes better.
  • the adhesive composition for organic fibers of the present invention comprises (A) a rubber latex having an unsaturated diene, (B) casein, and (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group, (D). It is characterized by containing one or more compounds selected from the group consisting of epoxide compounds and (E) polyphenols.
  • the epoxide compound and (E) the polyphenol can be mixed in any order.
  • the adhesive composition for organic fibers is subjected to the coating treatment of the organic fibers as soon as possible. Specifically, it is preferable that the adhesive composition for organic fibers is subjected to the coating treatment of organic fibers within 2 days after mixing the epoxide compound (D) with water, and more preferably within 1 day. ..
  • the mixed mass ratio [(A): (B)] (solid content conversion) of (A) a rubber latex having an unsaturated diene and (B) casein is particularly limited. However, it is preferably in the range of 100: 0.1 to 100: 25, and more preferably in the range of 100: 0.2 to 100: 5.
  • the mixed mass ratio is 100: 0.1 or more (if the ratio value is 1000 or less), (A) a rubber latex having an unsaturated diene is used as a core, and (B) casein micron around the core. This is because a film of a capsule can be formed and an adhesive layer having sufficient strength can be obtained. If the mixed mass ratio is 100:25 or less (if the ratio value is 4 or more), (A) a rubber latex having an unsaturated diene is used as a core, and (B) is formed around the rubber latex.
  • the film of the microcapsules of casein does not become too thick, and it is the above-mentioned adherend when the coated rubber composition which is the adherend of the organic fiber and the adhesive composition for the organic fiber are co-sulfurized and adhered.
  • the coated rubber composition and the rubber latex having (A) unsaturated diene are well compatible with each other, and as a result, between the coated rubber composition which is the adherend and the adhesive composition for organic fibers. This is because the initial process of bonding proceeds favorably.
  • a known water-soluble material capable of strengthening the film composed of (B) casein can be used in combination with ordinary coacervates.
  • electrolytes consisting of Arabic gum, carrageenan, CMCs, organic or inorganic salts, eg salts with cations such as sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, sulfates, phosphates, carbonates. Salts having anions such as salts and acetates can be used.
  • liquid substances that are water-soluble and in which the film-forming material dissolves less than water, such as ethanol, alcohols such as propanol, or isobutylene-maleic anhydride ring-opening.
  • Water-soluble polymers such as polymer salts can also be used.
  • the mixed mass ratio [(A): [(C) + (D) + (E)]] (in terms of solid content) with the compound selected from the group consisting of polyphenols is not particularly limited, but 100: It is preferably in the range of 5 to 100: 300, more preferably in the range of 100:10 to 100:150, and even more preferably in the range of 100:15 to 100:60.
  • the ratio of the rubber latex having (A) unsaturated diene in the adhesive composition for organic fibers becomes large. This is because the destructive resistance of the adhesive layer due to the adhesive composition for organic fibers can be sufficiently maintained, and the deterioration of the adhesiveness under strain can be prevented. Further, if the mixed mass ratio is 100: 300 or less (if the ratio value is 1/3 or more), the rubber latex having (A) unsaturated diene in the adhesive composition for organic fibers occupies.
  • the coated rubber composition which is an adherend of organic fibers
  • the adhesive composition for organic fibers are co-sulfurized and bonded
  • the ratio does not become too low, and the coated rubber composition, which is the adherend, is used.
  • the rubber latex having (A) unsaturated diene is well compatible, and as a result, the adhesiveness between the coated rubber composition which is the adherend and the adhesive composition for organic fibers is sufficiently sufficient. Because it will be expensive.
  • the above-mentioned (A) rubber latex having an unsaturated diene, (B) casein, (C) an aqueous compound having a (heat dissociative blocked) isocyanate group, (D) an epoxide compound, and (E) polyphenol are It is preferably aqueous. This is because water, which is less polluting to the environment, can be used as a solvent.
  • the organic fiber-rubber composite of the present invention is a composite of organic fibers and rubber, and is characterized in that the organic fibers are coated with the above-mentioned adhesive composition for organic fibers. As a result, good adhesiveness can be obtained without using resorcin, and an organic fiber-rubber composite having good environmental friendliness and workability can be obtained.
  • FIG. 4 is a schematic cross-sectional view showing an organic fiber cord-rubber composite of an example of the organic fiber-rubber composite of the present invention.
  • the outer radial outer surface of the organic fiber cord 1 is coated with the adhesive layer 32 according to the adhesive composition 2 for organic fibers of the present invention. Then, the organic fiber cord 1 is further adhered to the coated rubber composition 33 on the outer radial side thereof via the adhesive layer 32 by the adhesive composition 2 for organic fibers, and the organic fiber of the present invention-.
  • the rubber composite 31 is formed.
  • the form of the reinforcing material for the rubber article using the adhesive composition for organic fibers of the present invention may be a film, a short fiber, a non-woven fabric, or the like. ..
  • Organic Fiber-Rubber Complex Organic Fiber Code The organic fiber cord constituting the organic fiber-rubber composite of the present invention can be as described above.
  • the coated rubber composition constituting the organic fiber-rubber composite of the present invention preferably contains a rubber component mixed with various compounding agents 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).
  • the organic fiber-rubber composite of the present invention covers an organic fiber such as an organic fiber cord with the adhesive composition for organic fibers of the present invention to form an adhesive layer, and is contained in the above-mentioned adhesive composition for organic fibers.
  • the method of coating the organic fiber with the adhesive composition for organic fiber of the present invention is not particularly limited, but a method of immersing the organic fiber in the adhesive composition for organic fiber, the organic.
  • Examples include a method of applying the adhesive composition for fibers to the organic fibers by brushing, a method of spraying the adhesive composition for organic fibers on the organic fibers, and the like, and selecting an appropriate method as necessary. Can be done.
  • the organic fiber adhesive composition When the organic fiber is coated with the organic fiber adhesive composition, it is preferable to dissolve the organic fiber adhesive composition in various solvents to reduce the viscosity, because the coating becomes easy. It is environmentally preferable that the solvent for lowering the viscosity of the adhesive composition for organic fibers is mainly composed of water.
  • the thickness of the adhesive layer by the adhesive composition for organic fibers is not particularly limited, but is preferably 50 ⁇ m or less, more preferably 0.5 ⁇ m or more and 30 ⁇ m or less. ..
  • 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. Since 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. From the above, the average thickness of the adhesive composition layer is preferably 50 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 30 ⁇ m or less.
  • the concentration of the adhesive composition for organic fibers impregnated in the organic fibers is not particularly limited, but is 5.0% by mass or more in terms of solid content with respect to the mass of the organic fibers. It is preferably 25.0% by mass or less, and more preferably 7.5% by mass or more and 20.0% by mass or less.
  • the organic fiber coated with the adhesive composition for organic fiber is, for example, dried at a temperature of 100 ° C. or higher and 210 ° C. or lower, and then has a glass transition temperature (typically, the high temperature) of the polymer chain of the organic fiber. 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 molecular 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, the molecular mobility of the polymer chain of the organic fiber becomes good, and the adhesion is promoted in the adhesive composition for organic fiber.
  • the adhesive composition for organic fibers is such that the agent (for example, (C) (thermally dissociable blocked) aqueous compound having an isocyanate group) and the polymer chain of the organic fiber can sufficiently interact with each other. This is because a sufficient adhesive force between the organic fiber and the organic fiber can be obtained.
  • the organic fiber 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 cord, a cable, a filament, a filament chip, a cord fabric, and a canvas.
  • a cord made by twisting a plurality of filaments is preferably used as the resin material.
  • the organic fiber is a 66 nylon tire cord having a twist structure of 1400 dtex / 2, an upper twist number of 39 times / 10 cm, and a lower twist number of 39 times / 10 cm. It is preferably an organic fiber-rubber composite to which the composition is attached.
  • the organic fiber coated with the organic fiber adhesive composition is the coating of the rubber latex having (A) unsaturated diene in the organic fiber adhesive composition and the adherend of the organic fiber.
  • the rubber component in the rubber composition is co-vulcanized and adhered.
  • sulfur for co-vulcanization of the rubber component in the coated rubber composition
  • sulfur for example, sulfur, tetramethyltylalium disulfide, dipentamethylenetylalium tetrasulfide and other tyralium polysulfide compounds, 4,4-dithiomorpholin, p- Organic vulcanizing agents such as quinonedioxime, p, p'-dibenzoquinonedioxime, and cyclic sulfurimide
  • sulfur tetramethyltylalium disulfide
  • 4,4-dithiomorpholin for example, sulfur, tetramethyltylalium disulfide, dipentamethylenetylalium tetrasulfide and other tyralium polysulfide compounds
  • 4,4-dithiomorpholin for example, sulfur, tetra
  • various compounding agents 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 are used. , Can be appropriately blended.
  • the vulcanizing agent contained in the adherend of the synthetic resin material such as organic fibers and / or the adherend of the coated rubber composition is the adhesive composition for organic fibers.
  • the adhesive composition for organic fibers even in the bonding method in which the adhesive composition for organic fibers is crosslinked by the vulcanizing agent that has been transferred to the product, the effect of bonding can be obtained.
  • the tire of the present invention uses the organic fiber-rubber composite of the present invention. As a result, good adhesiveness can be obtained without using resorcin, and a tire with good environmental friendliness and workability can be obtained.
  • the organic fiber-rubber composite can be used as, for example, a reinforcing layer around a belt such as a carcass, a belt, a belt reinforcing layer, and a flipper.
  • the tire of the present invention may be obtained by vulcanizing after molding using an unvulcanized rubber composition depending on the type of tire to be applied, or semi-vulcanized rubber that has undergone a preliminary vulcanization step or the like is used. It may be obtained by further main vulcanization after molding.
  • organic fibers treated with the above-mentioned adhesive composition are used in any part of the tire, but other members are not particularly limited, and known members are used. be able to.
  • the tire of the present invention is preferably a pneumatic tire, and the gas to be filled in the pneumatic tire may be normal or air with adjusted oxygen partial pressure, nitrogen, argon, helium or the like. An inert gas can be used.
  • the above-mentioned adhesive composition for organic fibers of the present invention and the organic fiber-rubber composite of the present invention can be applied to all rubber articles such as conveyor belts, belts, hoses, and air springs in addition to the above tires. Can also be applied.
  • (A) vinylpyridine-styrene-butadiene copolymer latex as the 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.
  • (B) casein 5 g of the reagent name "casein (made of milk)" (powder solid) manufactured by Nakaraitesk Co., Ltd., which is an isoelectric precipitation casein (acid casein), is added to deionized water. While suspending in 70 g of water, add 25 g of the reagent name "1 mol / L ammonia water” (specified concentration solution for volumetric analysis) manufactured by Kanto Chemical Co., Ltd. as an alkali for neutralization and dissolution, and the liquid temperature is 55. It was dissolved at ° C. until it became transparent to prepare an aqueous solution having a casein solid content concentration of 5% by mass, and this aqueous solution was used for preparing an adhesive composition.
  • Latex-Aqueous Urethane Adhesive Composition (Comparative Example 2) >> The rubber latex having the (A) unsaturated diene and the aqueous compound having the (heat dissociable blocked) isocyanate group (C) are blended as shown in Table 2, and the solid content concentration of the adhesive composition is obtained. After adjusting the amount with water so as to be 18% by mass and mixing, the mixture was sufficiently stirred to obtain a latex-aqueous urethane adhesive composition (Comparative Example 2).
  • Latex-Epoxide Adhesive Composition (Comparative Example 3)
  • the rubber latex having (A) unsaturated diene and the above (D) epoxide compound are blended as shown in Table 2, and the amount of the adhesive composition is adjusted to 18% by mass with water. After adjusting and mixing, the mixture was sufficiently stirred to obtain a latex-epoxide adhesive composition (Comparative Example 3).
  • Latex-Polyphenol Adhesive Composition (Comparative Examples 4 and 5)
  • the rubber latex having (A) unsaturated diene and the above (E) polyphenol are blended as shown in Table 2, and the amount is adjusted with water so that the solid content concentration of the adhesive composition is 18% by mass. After adjusting and mixing, the mixture was sufficiently stirred to obtain a latex-polyphenol adhesive composition (Comparative Examples 4 and 5).
  • ⁇ Coating of tire cord with adhesive composition for each organic fiber As the organic fiber, a tire cord made of polyethylene terephthalate having a twist structure of 1670 dtex / 2, an upper twist number of 39 times / 10 cm, and a lower twist number of 39 times / 10 cm was used.
  • the tire cord was dipped in each of the organic fiber adhesive compositions of Comparative Examples 1 to 5 and Examples 1 to 6, and the concentration of the organic fiber adhesive composition impregnated in the tire cord was the mass of the organic fiber. It was adjusted to 3.8% by mass. Next, drying in the drying zone (150 ° C., 60 seconds), thermosetting the resin while applying tension (0.8 kg / piece) in the hot zone, and thermosetting while relaxing the above tension in the normalized zone (240 ° C., For 60 seconds), tire cords coated with the adhesive compositions for organic fibers of Comparative Examples 1 to 5 and Examples 1 to 6 were obtained.
  • ⁇ Tire code-Making rubber complex The tire cords coated with the adhesive compositions for organic fibers of Comparative Examples 1 to 5 and Examples 1 to 6 were embedded in an unvulcanized rubber composition and co-vulcanized at 155 ° C. for 20 minutes.
  • an unvulcanized rubber composition for coating a rubber composition containing natural rubber, styrene-butadiene rubber, carbon black, vulcanized chemicals and the like was used.
  • the mechanical stability (coagulation rate) of each organic fiber adhesive composition is determined by the Maron type mechanical stability tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) for the copolymer latex composition shown in JIS K6392-1995. The measurement was performed according to the method using the Marlon stability tester No. 2312-II).
  • Vinyl pyridine latex Vinyl pyridine-styrene-butadiene copolymer latex synthesized by the above method (solid content concentration 41% by mass) * B1) Acid casein: Made by Nakaraitesk Co., Ltd., reagent name "casein (milk)" (powder solid), etc.
  • Aqueous urethane compound manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "Elastron BN77 (F-2955D-1)" (blocking agent thermal dissociation temperature: about 160 ° C., pH 8.0, solid content concentration 31% by mass) (Thermal dissociable blocked)
  • Epoxide compound Manufactured by Nagase ChemteX Corporation, trade name “Denacol EX-614B” (molecular weight 949, epoxy equivalent 173, solid content concentration 10% by mass) ) Sorbitol polyglycidyl ether * E1)
  • Polyphenol manufactured by Tokyo Kasei Kogyo Co., Ltd., trade name "lignin (alkali)” (CAS Molecular: 8061-51-6) Partially desulfonated lignin sulfonic acid with reduced sulfonate degree Salt * E2) Polyphenol: Sigma-
  • an adhesive composition capable of ensuring desired adhesiveness without using resorcin, having excellent crosslinkability and not impairing workability during use, and organic fibers using the same. Rubber composites and tires can be provided. Therefore, the present invention can be used in the industrial field of manufacturing rubber articles such as tires.
  • Organic fiber cord 2 Adhesive composition for organic fiber 3: Immersion bath (dipping tank) 4: Organic fiber cord coated with an adhesive composition for organic fibers 5: Squeeze roll 6: Dry zone 7: Hot zone 8: Normalized zone 11: Rubber latex with unsaturated isocyanate 12: Casein 13: (Thermal dissociation) Sex blocked) Urethane resin formed by an aqueous urethane compound having an isocyanate group 14: Activated isocyanate group 15: Part that easily interacts with the organic fiber cord 16: Part that is difficult to diffuse into the organic fiber cord 20: Latex -Casein protective film effect 21: Rubber co-isocyanate adhesion 22: Casein-isocyanate cross-linking 23: Activated isocyanate cross-linking 24: Aqueous urethane-organic fiber interface effect 31: Organic fiber-rubber composite 32: Adhesive composition for organic fiber 33: Coated rubber composition 40: Water-dispersible (heat-dissociable blocked) is

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Abstract

La présente invention concerne une composition adhésive pour fibres organiques, ladite composition adhésive étant susceptible d'assurer une adhérence souhaitée sans faire appel à du résorcinol, tout en ayant un excellent caractère respectueux de l'environnement et sans dégrader l'aptitude au façonnage en cours d'utilisation ; un corps composite fibres organiques-caoutchouc ; et un pneu.　L'invention porte plus précisément sur une composition adhésive pour fibres organiques, ladite composition adhésive contenant au moins un composé qui est choisi dans le groupe consistant en (A) un latex de caoutchouc comprenant un diène insaturé, (B) de la caséine, (C) un composé aqueux ayant un groupe isocyanate (bloqué à dissociation thermique), (D) un composé époxyde et (E) un polyphénol, tout en ne contenant pas de résorcinol.
PCT/JP2021/042296 2020-12-23 2021-11-17 Composition adhésive pour fibres organiques, corps composite fibres organiques-caoutchouc et pneu WO2022137908A1 (fr)

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DE102022121145A1 (de) 2022-08-22 2024-02-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Dispersion, Verfahren zu ihrer Herstellung und Verwendung als Klebstoff für Holzwerkstoffe

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JPH05202343A (ja) * 1991-09-09 1993-08-10 Wacker Silicones Corp ゴム基材用の高接着性の塗料組成物、ゴム製品の製法及び加硫ゴム製品、着色タイヤ及び接着された製品
JP5746939B2 (ja) * 2011-09-15 2015-07-08 株式会社ブリヂストン 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
WO2018003572A1 (fr) * 2016-06-30 2018-01-04 ナガセケムテックス株式会社 Adhésif pour fibres organiques, et procédé de traitement de fibres organiques
US20200208023A1 (en) * 2018-12-27 2020-07-02 Far Eastern New Century Corporation Adhesive composition, organic fiber and treating method thereof, and method of forming organic fiber/rubber composite
WO2021220989A1 (fr) * 2020-04-30 2021-11-04 株式会社ブリヂストン Composition adhésive pour câbles à fibre organique, corps composite de câble à fibre organique- caoutchouc et pneumatique

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JPH05202343A (ja) * 1991-09-09 1993-08-10 Wacker Silicones Corp ゴム基材用の高接着性の塗料組成物、ゴム製品の製法及び加硫ゴム製品、着色タイヤ及び接着された製品
JP5746939B2 (ja) * 2011-09-15 2015-07-08 株式会社ブリヂストン 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
WO2018003572A1 (fr) * 2016-06-30 2018-01-04 ナガセケムテックス株式会社 Adhésif pour fibres organiques, et procédé de traitement de fibres organiques
US20200208023A1 (en) * 2018-12-27 2020-07-02 Far Eastern New Century Corporation Adhesive composition, organic fiber and treating method thereof, and method of forming organic fiber/rubber composite
WO2021220989A1 (fr) * 2020-04-30 2021-11-04 株式会社ブリヂストン Composition adhésive pour câbles à fibre organique, corps composite de câble à fibre organique- caoutchouc et pneumatique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022121145A1 (de) 2022-08-22 2024-02-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Dispersion, Verfahren zu ihrer Herstellung und Verwendung als Klebstoff für Holzwerkstoffe
DE102022121145B4 (de) 2022-08-22 2024-03-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Dispersion, Verfahren zu ihrer Herstellung und Verwendung als Klebstoff für Holzwerkstoffe

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