WO2022137908A1 - Adhesive composition for organic fibers, organic fiber-rubber composite body, and tire - Google Patents

Adhesive composition for organic fibers, organic fiber-rubber composite body, and tire 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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French (fr)
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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Priority to JP2022571968A priority Critical patent/JPWO2022137908A1/ja
Publication of WO2022137908A1 publication Critical patent/WO2022137908A1/en

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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

Abstract

The present invention provides: an adhesive composition for organic fibers, said adhesive composition being capable of ensuring a desired adhesiveness without using resorcin, while having excellent environmental friendliness and not deteriorating the workability when in use; an organic fiber-rubber composite body; and a tire.　An adhesive composition for organic fibers, said adhesive composition containing at least one compound that is selected from the group consisting of (A) a rubber latex comprising an unsaturated diene, (B) casein, (C) an aqueous compound having a (thermally dissociative blocked) isocyanate group, (D) an epoxide compound and (E) a polyphenol, while containing no resorcin.

Description

有機繊維用接着剤組成物、有機繊維－ゴム複合体およびタイヤAdhesive compositions for organic fibers, organic fiber-rubber complexes and tires
　本発明は、有機繊維用接着剤組成物（以下、単に「接着剤組成物」とも称する）、有機繊維－ゴム複合体およびタイヤに関するものである。 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.
　従来、タイヤ等のゴム物品を補強する目的において、ナイロン繊維やポリエステル繊維等からなるタイヤコード等の有機繊維と、タイヤ用ゴム組成物等のゴム組成物とを接着させて、有機繊維－ゴム複合体とすることが行われている。そして、上記接着には、有機繊維を接着剤組成物で被覆し、ゴム組成物に埋設して、ゴム組成物と共加硫する手法が汎用されている。 Conventionally, for the purpose of reinforcing rubber articles such as tires, 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. Then, for the above-mentioned adhesion, 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.
　また、上記有機繊維を上記接着剤組成物で被覆する工程においては、接着剤組成物の粘度を調整する目的で一般的に溶媒を用いるが、該工程で溶媒が揮発するために、上記溶媒としては環境負荷の少ない水を用いることが好ましい。さらに、浸漬により上記有機繊維のコードなどを上記接着剤組成物で被覆する場合には、接着剤組成物を浸漬により塗布できる程度の低粘度にすることが必要である。 Further, in the step of coating the organic fiber with the adhesive composition, 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.
　一般的に、水性、すなわち、水に溶解あるいは分散できる性質を持たせた水系接着剤組成物に含まれる成分は、極性を持つ分子構造を有する必要がある。しかし、一方で、被着体となるゴムや有機繊維コード基材等の高分子材料は極性が低く、ゴムや有機繊維コード基材等の表面の極性と接着剤組成物に含まれる成分の極性との差が大きくなると、接着し難くなる。従って、上記水系接着剤組成物をゴム物品用の接着剤組成物として用いるためには、上記水系接着剤組成物に含まれる成分については、水性であるために極性を持つ必要がある反面、このことにより被着体の極性との間に差が生じて接着性が低下しないような極性の制御が必要である。そこで、これらの背反する要請を両立できる機能を有する水系の接着剤組成物が好適に用いられている。 In general, 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. However, on the other hand, 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. As a result, it is necessary to control the polarity so that there is a difference between the polarity and the polarity of the adherend and the adhesiveness does not deteriorate. Therefore, a water-based adhesive composition having a function of achieving both of these contradictory requirements is preferably used.
　ここで、上記有機繊維コード等を上記接着剤組成物で被覆する工程に関し、上記有機繊維コードを接着剤組成物に浸漬する場合の工程の一例を、図１を用いて説明する。 Here, regarding the step of coating the organic fiber cord or the like with the adhesive composition, an example of the step of immersing the organic fiber cord in the adhesive composition will be described with reference to FIG. 1.
　有機繊維コード１は、巻出しロールから巻出され、ロールにより搬送されて、有機繊維コード用接着剤組成物２が入った浸漬用浴槽（ディッピング槽）３にて、上記有機繊維用接着剤組成物２中に浸漬される。有機繊維用接着剤組成物２で被覆された有機繊維コード４は、上記浸漬用浴槽３から引き上げられ、絞りロール５により余分な有機繊維用接着剤組成物２が取り除かれる。次いで、有機繊維用接着剤組成物２で被覆された有機繊維コード４は、ロールによりさらに搬送されて、乾燥ゾーン６で乾燥され、ホットゾーン７では張力の付与により延伸されつつ樹脂の熱硬化を受け、ノルマライズゾーン８では目的の強伸度物性になるように上記張力を精度よく調整して標準化（ノルマライジング）されながら樹脂の熱硬化を受け、ゾーン外で空冷された後に、巻取ロールに巻き取られる。このようにして、上記有機繊維コードは、上記接着剤組成物で被覆される。 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. Next, 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. In the normalized zone 8, 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.
　上記接着剤組成物としては、従来、レゾルシン、ホルムアルデヒドおよびゴムラテックスを含む混合液を熟成させて得られるＲＦＬ（レゾルシン－ホルムアルデヒド－ラテックス）接着剤組成物、または、このＲＦＬ接着剤組成物に特定の接着促進剤を混合した接着剤組成物が用いられてきた（特許文献１～４参照）。 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).
　周知のように、ゴム業界では、水分散性のゴムラテックス成分と、水溶性であるレゾルシンとホルムアルデヒドを混合して熟成することで得られた水系のフェノール樹脂と、からなる接着剤組成物（特許文献１）が、被着体となるゴムとの接着と、有機繊維コード等の極性が少ない基材表面との接着と、を両立する機能を有することが見出され、世界的に広く用いられている。上記ＲＦＬ接着剤組成物による接着においては、ゴムラテックス成分により被着ゴム側と共加硫で接着し、一方、有機繊維基材との接着性を有するレゾルシンとホルムアルデヒドの縮合物からなるフェノール系樹脂成分により、被着基材側と接着する。 As is well known, in the rubber industry, 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. ing. In the bonding with the RFL adhesive composition, 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.
　ここで、レゾルシンが好ましく用いられている理由は、被着体との接着性が高い樹脂種であるフェノール系縮合樹脂を提供できるとともに、水溶性を得るためにフェノール環に導入される極性官能基が、極性が比較的小さく立体障害となりにくい水酸基であって、有機繊維基材側と接着性が高い樹脂成分を提供できるためである。 Here, the reason why 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. However, this is because it is possible to provide 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.
　また、上記ＲＦＬ接着剤組成物は、塩基性組成物の存在下で、レゾルシンと、ホルムアルデヒドと、重合の際に乳化剤としてロジン酸等を用いたゴムラテックスと、を混合して熟成して得られる。これにより、水溶したレゾルシンとホルムアルデヒドが塩基下でのレゾール型縮合反応で縮合するとともに（特許文献２を参照）、ラテックス表面のロジン酸が、レゾール型のフェノール－ホルムアルデヒド付加縮合体の末端のメチロール基と付加縮合すると推察されている（非特許文献１を参照）。 Further, 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. .. As a result, 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. (See Non-Patent Document 1).
　この熟成により、ラテックスがロジン酸を介してレゾール型レゾルシン－ホルムアルデヒド縮合物と架橋して、接着が強化され、ラテックスが水性樹脂と複合してカプセル化した保護コロイドとなり、図１に示されるような装置において接着剤組成物の処理を行う際に、ラテックスのゴム粘着性が抑制されるため、装置に対する接着剤組成物の粘着による汚れが少なくなる。 During this aging, 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. When the adhesive composition is processed in the apparatus, 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.
　そして、上記ＲＦＬ接着剤組成物に添加する接着促進剤としては、水系接着剤組成物により、有機繊維コード材料等の極性が少ない基材表面との接着を向上させるために、水性、すなわち、水に溶解あるいは分散できる性質を有する接着促進剤が用いられてきた。 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.
　水分散性の上記接着促進剤としては、粒子径が０．０１～０．５０μｍであるメチレンジフェニルジイソシアネート等の（ブロックド）イソシアネート（特許文献３を参照）や、クレゾールノボラック型多官能エポキシ樹脂等の非水溶性であるフェノール系・ノボラック型樹脂の水分散粒子（特許文献４を参照）等が使用されている。 Examples of the water-dispersible adhesive accelerator include (blocked) isocyanates such as methylenediphenyldiisocyanate having a particle size of 0.01 to 0.50 μm (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.
　また、水溶性の基を含む上記接着促進剤としては、レゾルシンとホルムアルデヒドとをノボラック化反応させて得られるノボラック型縮合物の水酸化ナトリウム溶液（特許文献５を参照）、クロロフェノール類とホルムアルデヒドのノボラック型縮合物のアンモニウム溶液等の塩基性物質の存在下で水に溶解するフェノール系樹脂類、あるいは、（熱解離性ブロックド）イソシアネート基と自己水溶性である基を有する水性ウレタン化合物（特許文献６を参照）等が、ＲＦＬ接着剤組成物と併せて使用されている。 Further, as the above-mentioned adhesion promoter containing a water-soluble group, a novolak-type condensate sodium hydroxide solution (see Patent Document 5) 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.
　ところが、近年、ＲＦＬ接着剤組成物において水溶性の成分として用いられてきたレゾルシンについて、環境負荷低減の観点から、使用量の削減が求められるようになってきている。 However, in recent years, the amount of resorcin used as a water-soluble component in RFL adhesive compositions has been required to be reduced from the viewpoint of reducing the environmental load.
　これに対応するために、レゾルシンを含まず、水を溶媒とした系の接着剤組成物が、様々に検討されて提案されている。 In order to deal with this, various adhesive compositions that do not contain resorcin and use water as a solvent have been studied and proposed.
　例えば、ゴムラテックスとブロックドイソシアネート化合物とエポキシド化合物および硬化剤のアミノ系化合物からなる接着剤組成物（特許文献７を参照）、または、（熱解離性ブロックド）イソシアネート基を有するウレタン樹脂、エポキシド化合物、オキサゾリン基を有する高分子、数平均分子量１，０００～７５，０００の塩基性触媒及びゴムラテックスを含む有機繊維コード用接着剤組成物（特許文献８を参照）等が、レゾルシンを含まない接着剤組成物として、知られている。 For example, 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 (see Patent Document 8) does not contain isocyanate. It is known as an adhesive composition.
米国特許第２，１２８，２２９号明細書US Pat. No. 2,128,229 特開２００５－２６３８８７号公報Japanese Unexamined Patent Publication No. 2005-263887 特開２００６－３７２５１号公報Japanese Unexamined Patent Publication No. 2006-3751 特開平９－１２９９７号公報Japanese Unexamined Patent Publication No. 9-12997 国際公開第９７／０１３８１８号International Publication No. 97/013818 特開２０１１－２４１４０２号公報Japanese Unexamined Patent Publication No. 2011-241402 国際公開第２０１０／１２５９９２号International Publication No. 2010/125992 特開２０１３－６４０３７号公報Japanese Unexamined Patent Publication No. 2013-64037
　しかしながら、上記のようなレゾルシンを含まない接着剤組成物を使用すると、接着剤液のせん断歪下での機械的安定性の指標として測定されるゴムラテックスの粘着性が高くなってしまう。その結果、例えば、図１に示すような、上記有機繊維コード１を上記有機繊維用接着剤組成物２で被覆して乾燥・熱硬化させる工程において、絞りロール５や乾燥ゾーン６のロール等に対する当該有機繊維用接着剤組成物２の付着が多くなり、当該工程の作業性が悪くなるという新たな問題が発生した。 However, when the adhesive composition containing no resorcin as described above is 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. As a result, for example, in the step of coating the organic fiber cord 1 with the organic fiber adhesive composition 2 and drying / thermosetting the organic fiber cord 1 as shown in FIG. 1, 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.
　また、このようなレゾルシンを含まない接着剤組成物は、上記装置に対する付着によって接着剤被覆の表面が荒れるために接着性が低下し易く、さらに、被覆ゴム組成物中のラテックス成分と接着剤組成物中のレゾルシン・ホルムアルデヒド縮合物との間の架橋がそもそも得られないために、従来のＲＦＬ接着剤組成物に比べて接着性が低下するという課題も有していた。 Further, in such an adhesive composition containing no resorcin, 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.
　さらにまた、上記のようなレゾルシンを含まない接着剤組成物は、当該接着剤組成物で被覆された有機繊維コードのコード強力の低下をもたらすという課題も有していた。 Furthermore, 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.
　そこで本発明の目的は、レゾルシンを用いることなく所望の接着性を確保することができ、環境性に優れるとともに、使用時における作業性を損なうこともない有機繊維用接着剤組成物、有機繊維－ゴム複合体およびタイヤを提供することにある。 Therefore, 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.
　本発明者は、上記課題を解決するべく、有機繊維用接着剤組成物の組成について鋭意研究を重ねた。その結果、（Ａ）所定のゴムラテックスとともに、（Ｂ）カゼインと、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物および（Ｅ）ポリフェノールのうちの１種以上と、を配合することで、レゾルシンを用いることなく所望の接着性を確保することができ、使用時における作業性を損なうこともない接着剤組成物が得られることを見出して、本発明を完成するに至った。 The present inventor has conducted extensive research on the composition of the adhesive composition for organic fibers in order to solve the above problems. As a result, 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. We have found that by blending the above and above, a desired adhesiveness can be ensured without using resorcin, and an adhesive composition that does not impair workability during use can be obtained. It was completed.
　すなわち、本発明の有機繊維用接着剤組成物は、（Ａ）不飽和ジエンを有するゴムラテックス、（Ｂ）カゼイン、並びに、
　下記（Ｃ）～（Ｅ）：
　（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、
　（Ｄ）エポキシド化合物、および、
　（Ｅ）ポリフェノール
からなる群から選択される１種以上の化合物を含み、レゾルシンを含まないことを特徴とするものである。 That is, 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.
　本発明の有機繊維－ゴム複合体は、有機繊維とゴムとの複合体であって、該有機繊維が、上記有機繊維用接着剤組成物により被覆されていることを特徴とするものである。 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.
　本発明のタイヤは、上記有機繊維－ゴム複合体を用いたことを特徴とするものである。 The tire of the present invention is characterized by using the above-mentioned organic fiber-rubber composite.
　本発明によれば、レゾルシンを用いることなく所望の接着性を確保することができ、環境性に優れるとともに、使用時における作業性を損なうこともない有機繊維用接着剤組成物、有機繊維－ゴム複合体およびタイヤを提供できる。 According to the present invention, 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.
浸漬処理により、有機繊維コードを有機繊維用接着剤組成物で被覆する工程の一例を示す概略図である。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）芳香環を有するポリイソシアネートと活性水素基を１個以上有するブロック剤との付加生成物からなる水分散性（熱解離性ブロックド）イソシアネート化合物を用いた場合の、本発明の一実施形態に係る有機繊維用接着剤組成物による接着性向上の原理を示す概略説明図である。(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. It is a schematic explanatory drawing which shows the principle of the adhesiveness improvement by the adhesive composition for organic fiber which concerns on one Embodiment. （Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物を用いた場合の、本発明の一実施形態に係る有機繊維用接着剤組成物による接着性向上の原理を示す概略説明図である。(C-2) (Heat Dissociative Blocked) A schematic description showing the principle of improving the adhesiveness of the adhesive composition for organic fibers according to the embodiment of the present invention when an aqueous urethane compound having an isocyanate group is used. It is a figure. 本発明の有機繊維－ゴム複合体の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the organic fiber-rubber composite of this invention.
　以下に、本発明の有機繊維用接着剤組成物、有機繊維－ゴム複合体およびタイヤを、その実施形態に基づき、詳細に例示説明する。これらの記載は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。 Hereinafter, the adhesive composition for organic fibers, the organic fiber-rubber composite, and the tire of the present invention will be illustrated in detail based on the embodiments thereof. These descriptions are for the purpose of exemplifying the present invention and do not limit the present invention in any way.
　本明細書にて、範囲を表す場合、特に記載がない限り、その範囲の端も、その範囲のうちに含まれるものとする。 When expressing a range in this specification, unless otherwise specified, the end of the range is also included in the range.
［有機繊維用接着剤組成物］
　本発明の有機繊維用接着剤組成物は、（Ａ）不飽和ジエンを有するゴムラテックス、（Ｂ）カゼイン、並びに、
　下記（Ｃ）～（Ｅ）：
　（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、
　（Ｄ）エポキシド化合物、および、
　（Ｅ）ポリフェノール
からなる群から選択される１種以上の化合物を含み、レゾルシンを含まないことを特徴とする。 [Adhesive composition for organic fibers]
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.
　本発明の有機繊維用接着剤組成物によれば、上記構成としたことで、レゾルシンを用いることなく、有機繊維と被覆ゴム組成物との間の接着性を良好に確保することができる。本発明においては、（Ａ）不飽和ジエンを有するゴムラテックスと、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物および（Ｅ）ポリフェノールからなる群から選択される１種以上の化合物とが、有機繊維と被覆ゴム組成物の接着性の向上に寄与する。また、本発明の有機繊維用接着剤組成物においては、（Ｂ）カゼインを用いたことで、接着剤液のせん断歪下での機械的安定性として測定されるゴムラテックスの粘着性を抑制することにより、有機繊維を接着剤組成物で被覆して乾燥・熱硬化させる工程において、ロール等に対する接着剤組成物の付着を抑制することができ、作業性が良好となる。さらに、本発明の有機繊維用接着剤組成物によれば、レゾルシンを含まないことで、環境負荷を低減できる。 According to the adhesive composition for organic fibers of the present invention, the above configuration makes it possible to satisfactorily secure the adhesiveness between the organic fibers and the coated rubber composition without using resorcin. In the present invention, 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. Further, in 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.
　また、本発明の接着剤組成物は、さらに、ホルムアルデヒドを含まないことが好ましい。 Further, it is preferable that the adhesive composition of the present invention does not contain formaldehyde.
＜有機繊維コード＞
　本発明の有機繊維用接着剤組成物に係る有機繊維の一例の有機繊維コードとは、タイヤ等のゴム物品の強度を補うために使用されるものである。上記有機繊維コードを補強材として使用する際には、まず、紡糸された有機繊維の原糸を撚糸することで有機繊維コードとする。そして、当該有機繊維コードを、接着剤組成物を用いて、当該有機繊維コードを被覆するゴムに埋設して加硫を行い接着させることにより、有機繊維－ゴム複合体を作製し、この有機繊維－ゴム複合体を、タイヤ等のゴム物品の補強部材として使用することができる。 <Organic fiber cord>
The 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. When 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.
　上記有機繊維の材質としては、特に限定されないが、ポリエステル、６－ナイロン、６，６－ナイロン、４，６－ナイロン等の脂肪族ポリアミド繊維、人造フィブロイン繊維等のタンパク質繊維、ポリケトン繊維、ポリノナメチレンテレフタルアミド、パラフェニレンテレフタルアミドに代表される芳香族ポリアミド繊維、アクリル繊維、炭素繊維、レーヨン、リヨセル等のセルロース繊維に代表される繊維材料を挙げることができる。これらのうちでも、ポリエステル、６－ナイロン、６，６－ナイロンが好ましく、ポリエステルが特に好ましい。 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. Examples thereof include aromatic polyamide fibers typified by methylene terephthalamide and paraphenylene terephthalamide, and fiber materials typified by cellulose fibers such as acrylic fibers, carbon fibers, rayon and lyocell. Among these, polyester, 6-nylon, 6,6-nylon are preferable, and polyester is particularly preferable.
　上記ポリエステルの材料は、主鎖中にエステル結合を有する高分子であり、より詳しくは、主鎖中の繰り返し単位の結合様式の８０％以上がエステル結合様式のものである。上記ポリエステルの例としては、特に限定されるものではないが、エチレングリコール、プロピレングリコール、ブチレングリコール、メトキシポリエチレングリコールおよびペンタエリスリトール等であるグリコール類と、テレフタル酸、イソフタル酸およびそれらのジメチル体等であるジカルボン酸類とのエステル化反応またはエステル交換反応によって縮合して得られるものが挙げられる。最も代表的なポリエステルは、ポリエチレンテレフタレートである。 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. Examples of 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.
　上記有機繊維コードは、特に、タイヤやコンベヤベルト等のゴム物品を補強する目的において、複数の単繊維フィラメントを撚り合わせてなる有機繊維コードであることが好ましい。また、上記有機繊維コードは、上撚りの単繊維フィラメントと下撚りの単繊維フィラメントとを撚り合わせてなる有機繊維コードであることが好ましい。この場合、下撚りの撚係数が１，３００以上、２，５００以下、および／または、上撚りの撚係数が９００以上、１，８００以下であることが、より好ましい。 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.
＜（Ａ）不飽和ジエンを有するゴムラテックス＞
　本発明の有機繊維用接着剤組成物における（Ａ）不飽和ジエンを有するゴムラテックスは、硫黄による加硫性を有する不飽和ジエンを含むゴムラテックスを意味する。 <(A) Rubber latex with unsaturated diene>
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.
　本発明の一実施形態において、有機繊維用接着剤組成物に含まれる上記（Ａ）不飽和ジエンを有するゴムラテックスが示す作用の原理の一例を、図２および図３を参照しつつ、説明する。不飽和ジエンを有するゴムラテックス１１は、有機繊維用接着剤組成物２による接着剤層３２とその被着体である被覆ゴム組成物３３とを接着させるための成分である。上記不飽和ジエンを有するゴムラテックス１１は、上記被着体である被覆ゴム組成物３３に含まれるゴムポリマーと相溶し、さらに、不飽和ジエン部位が共加硫することによって、ゴム共加硫接着２１を形成する。その結果、（Ａ）不飽和ジエンを有するゴムラテックスを含有する本発明の有機繊維用接着剤組成物によれば、有機繊維と被覆ゴム組成物の間を、良好に接着することができる。 In one embodiment of the present invention, an example of the principle of action exhibited by 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. As a result, according to (A) 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.
　上記（Ａ）不飽和ジエンを有するゴムラテックスとしては、限定されるものではないが、スチレン－ブタジエン共重合体ゴムラテックス、ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックス、カルボキシル基変性スチレン－ブタジエン共重合体ゴムラテックス、ニトリルゴムラテックス、クロロプレンゴムラテックス等の不飽和ジエンを有する合成ゴムラテックス；フィールドラテックス、アンモニア処理ラテックス、脱タンパク質ラテックス等の天然ゴムラテックスを挙げることができる。これらを１種単独で使用しても、２種以上を組み合わせて使用してもよい。 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.
　上記のうちでも、ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックスが好ましい。ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックスは、従来より有機繊維用接着剤組成物や、タイヤ等の物品においても汎用されてきたゴムラテックスであり、本発明の有機繊維用接着剤組成物においても、接着剤層と被着ゴムとの間に、良好な結合をもたらし、比較的柔軟でかつ可撓性を有するとの利点によって、上記接着剤層が分裂することなく、有機繊維の変形を伴うことも可能にするからである。 Among the above, 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.
　また、本発明の有機繊維用接着剤組成物中の固形分全体に占める、上記（Ａ）不飽和ジエンを有するゴムラテックスの含有量（固形分含有率）は、特に限定されるものではないが、２５質量％以上であることが好ましく、４０質量％以上であることがより好ましく、５０質量％以上であることがさらに好ましい。また、上記（Ａ）不飽和ジエンを有するゴムラテックスの含有量は、９５質量％以下であることが好ましく、９０質量％以下であることがより好ましく、８５質量％以下であることがさらに好ましい。上記（Ａ）不飽和ジエンを有するゴムラテックスの含有量が、２５質量％以上であると、被着ゴム組成物と接着剤組成物に含まれるゴムラテックスとのゴムポリマー同士の相容がより適度となり、有機繊維－ゴム複合体における被覆ゴムの付着状態がより優れるものとなるからである。一方、上記（Ａ）不飽和ジエンを有するゴムラテックスの含有量が、９５質量％以下であると、上記接着剤組成物中、他成分として含まれる樹脂成分の量を、相対的に一定以上に確保することができ、その結果、接着剤層の耐凝集破壊抗力が十分確保され、接着剤層内での破壊が起こり難くなることで、十分な接着性を得ることができるものとなるからである。 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. This is because the adhered state of the coated rubber in the organic fiber-rubber composite becomes more excellent. On the other hand, when 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.
　上記（Ａ）不飽和ジエンを有するゴムラテックスは、例えば、水にロジン酸カリウム等の乳化剤を溶解させた後、これに、単量体の混合物を添加し、さらに、リン酸ナトリウム等の電解質および過酸化物類等を重合開始剤として加えて、重合を行い、その後、所定の転化率に達した後、電荷移動剤を加え、重合を停止させ、さらに、残留する単量体を除去することによって、得ることができる。また、重合の際には、連鎖移動剤を使用することも好ましい。 For 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. 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.
　上記乳化剤としては、脂肪酸のアルカリ金属塩、ロジン酸のアルカリ金属塩、ホルムアルデヒド縮合ナフタレンスルホン酸ナトリウム、高級アルコールの硫酸エステル、アルキルベンゼンスルホン酸塩、脂肪族スルホン酸塩等のアニオン性界面活性剤、あるいは、ポリエチレングリコールのアルキルエステル型、アルキルエーテル型、アルキルフェニルエーテル型等のノニオン性界面活性剤のうちの１種あるいは２種以上が用いられる。 Examples of the emulsifier 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 , One or more of nonionic surfactants such as alkyl ester type, alkyl ether type and alkyl phenyl ether type of polyethylene glycol are used.
　これらの乳化剤のうちでも、ロジン酸の金属塩、特には、ロジン酸のアルカリ金属塩を含むことが好ましく、これは単独、すなわち、１種類のみで用いることもでき、他の乳化剤と２種以上で組み合わせて併用することもできる。ロジン酸は、松脂等から得られる３環性ジテルペン類を主成分として、よく似た化学構造の樹脂酸の混合物である。これら樹脂酸は、３つの環構造、２つの二重結合、１つのカルボキシル基を持っており、二重結合部分は、不飽和カルボン酸あるいはレゾール型フェノール樹脂のメチロール末端と、カルボキシル基部分でエステル化するなどの反応性に富んだ官能基を持っている。 Among these emulsifiers, it is preferable to contain a metal salt of logonic acid, particularly an alkali metal salt of logonic acid, which can be used alone, that is, only one kind, and two or more kinds with other emulsifiers. It can also be used in combination with. 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.
　このような乳化剤の使用量は、ラテックス重合に用いられる全単量体の１００質量部に対し、通常、０．１～８質量部であり、好ましくは１～５質量部である。 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.
　上記重合開始剤としては、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性開始剤、レドックス系開始剤、または、過酸化ベンゾイル等の油溶性開始剤が使用できる。中でも、過硫酸カリウムを用いることが好ましい。 As the polymerization initiator, for example, 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.
　上記連鎖移動剤としては、例えば、ｎ－ヘキシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ドデシルメルカプタン、ｎ－オクチルメルカプタン、ｎ－テトラデシルメルカプタン、ｔ－ヘキシルメルカプタン等の単官能アルキルメルカプタン類；１，１０－デカンジチオール、エチレングリコールジチオグリコレート等の２官能メルカプタン類；１，５，１０－カンジトリチオール、トリメチロールプロパントリスチオグリコレート等の３官能メルカプタン類；ペンタエリスリトールテトラキスチオグリコレート等の４官能メルカプタン類；ジスルフィド類；四塩化炭素、四臭化炭素、臭化エチレン等のハロゲン化合物；α－メチルスチレンダイマー、ターピノーレン、α－テルピネン、ジペンテン、アリルアルコール等が使用できる。これらは、単独または２種以上を組み合わせて用いられる。 Examples of the chain transfer agent 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; α-methylstyrene dimer, turpinolene, α-terpinene, dipentene, allyl alcohol and the like can be used. These may be used alone or in combination of two or more.
　これらの連鎖移動剤のうち、好ましくはアルキルメルカプタンが挙げられ、より好ましくはｎ－オクチルメルカプタン、ｔ－ドデシルメルカプタンが挙げられる。中でも、ｔ－ドデシルメルカプタンを用いることが好ましい。 Among these chain transfer agents, 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.
　このような連鎖移動剤の使用量は、ラテックス重合に用いられる全単量体の１００質量部に対し、通常、０．０１～５質量部であり、好ましくは０．１～３質量部である。 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. ..
　なお、上記ラテックスには、上記各成分以外に、必要に応じて、ヒンダードフェノール類等の老化防止剤、シリコーン系、高級アルコール系、鉱物油系の消泡剤、反応停止剤、凍結防止剤等の汎用の添加剤を使用してもよい。 In addition to the above components, 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. General-purpose additives such as may be used.
＜＜ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックス＞＞
　上記ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックスは、ビニルピリジン系単量体と、スチレン系単量体と、共役ジエン系ブタジエン単量体とを、三元共重合させたものであるが、これら単量体に共重合可能な他の単量体を更に含ませてもよい。 << Vinyl Pyridine-Styrene-butadiene Copolymer Rubber Latex >>
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.
　ここで、上記ビニルピリジン系単量体は、ビニルピリジンと、該ビニルピリジン中の水素原子が置換基で置換された置換ビニルピリジンとを包含する。このようなビニルピリジン系単量体としては、２－ビニルピリジン、３－ビニルピリジン、４－ビニルピリジン、２－メチル－５－ビニルピリジン、５－エチル－２－ビニルピリジン等が挙げられ、これらの中でも、２－ビニルピリジンが好ましい。これらビニルピリジン系単量体は、１種単独で使用しても、２種以上を組み合わせて使用してもよい。 Here, 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. Examples of such 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.
　上記スチレン系単量体は、スチレンと、該スチレン中の水素原子が置換基で置換された置換スチレンとを包含する。上記スチレン系単量体としては、スチレン、α－メチルスチレン、２－メチルスチレン、３－メチルスチレン、４－メチルスチレン、２，４－ジイノプロピルスチレン、２，４－ジメチルスチレン、４－ｔ－ブチルスチレン、ヒドロキシメチルスチレン等が挙げられ、これらの中でも、スチレンが好ましい。これらスチレン系単量体は、１種単独で使用しても、２種以上を組み合わせて使用してもよい。 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, α-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.
　上記共役ジエン系ブタジエン単量体としては、１，３－ブタジエン、２－メチル－１，３－ブタジエン等の脂肪族共役ブタジエン化合物が挙げられ、これらの中でも、１，３－ブタジエンが好ましい。これら共役ジエン系ブタジエン単量体は、１種単独で使用しても、２種以上を組み合わせて使用してもよい。 Examples of the conjugated diene-based butadiene monomer 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.
　上記ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックスの合成には、公知の方法を利用することができ、具体的には、例えば、本発明者らの検討による特開平９－７８０４５号公報に記載の方法を利用することができる。そして、それらの方法を利用して、ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックスの同一粒子内で、組成比が均一あるいは異なる共重合体等、様々な組成や粒子内構造を持たせることができる。 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.
　上記ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックスについて、同一粒子内で均一な組成の単量体混合比を有する共重合体の市販品としては、日本ゼオン（株）製のＮｉｐｏｌ　２５１８、日本エイアンドエル（株）製のピラテックス等が挙げられる。また、同一粒子内で異なる組成の単量体混合比を有する共重合体の市販品としては、ＪＳＲ（株）製のＶ０６５８等が挙げられる。これらはいずれも、本発明の有機繊維用接着剤組成物の（Ａ）不飽和ジエンを有するゴムラテックスとして、使用することができる。 Regarding 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.
　上記ビニルピリジン－スチレン－ブタジエン共重合体ゴムラテックスでは、ビニルピリジン：スチレン：ブタジエンの単量体比は、特に限定されるものではないが、ビニルピリジン－スチレン－ブタジエン共重合体粒子を構成する共重合体のうちに、ビニルピリジン５～２０質量％、スチレン１０～４０質量％、ブタジエン４５～７５質量％からなる単量体混合物を重合した共重合体を含むことが好ましい。ビニルピリジンが、５質量％以上であれば、ゴム成分内で加硫促進効果のあるピリジン部位が適量となり、硫黄による架橋度が増すと接着剤層全体の接着力がより向上し、２０質量％以下であれば、ゴムの架橋度が過加硫になることもなく、硬い接着剤とすることができるからである。また、スチレンが、１０質量％以上であれば、ラテックス粒子および接着剤層の強度を十分なものとし、接着力がより向上し、４０質量％以下であれば、接着剤層と被着ゴムとの共加硫性を適度にしながら、やはり接着力を確保することにつながるからである。さらに、ブタジエンが、４５質量％以上であれば、より十分な架橋を形成することが可能となり、７５質量％以下であれば、架橋を適度として、体積およびモジュラスの変化による耐久性を良好に確保することができるからである。ビニルピリジン：スチレン：ブタジエンの単量体混合物の組成比は、好適には例えば、１５：１５：７０とすることができる。 In the vinyl pyridine-styrene-butadiene copolymer rubber latex, 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. When vinyl pyridine is 5% by mass or more, 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. Further, if the amount of butadiene is 45% by mass or more, more sufficient cross-linking can be formed, and if it is 75% by mass or less, the cross-linking is moderate and durability due to changes in volume and modulus is sufficiently ensured. Because it can be done. The composition ratio of the vinyl pyridine: styrene: butadiene monomer mixture can be preferably, for example, 15:15:70.
＜（Ｂ）カゼイン＞
　本発明の有機繊維用接着剤組成物における（Ｂ）カゼインとしては、一般的に市販されているものを使用でき、本発明の有機繊維用接着剤組成物を得られるものである限り、特に限定されない。 <(B) Casein>
As the 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.
　（Ｂ）カゼインとしては、酸カゼイン、具体的には、塩酸カゼイン、硫酸カゼイン、レンネットカゼイン、ラクチックカゼインまたはこれらの変性化合物を例示できる。カゼインは、カゼイン塩であっても構わない。カゼイン塩は、酸カゼインを中和剤で処理して乾燥させることにより得られる生成物であり、使用される中和剤に応じて、カゼインナトリウム、カゼインカリウム、カゼインカルシウムおよびカゼイン塩混合物が挙げられる。 Examples of (B) casein 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. ..
　ここで、上記（Ｂ）カゼインは、乳に多く含まれるリンタンパク質である。また、上記カゼインは、通常、カゼインミセルとして存在して乳中に含まれている、リンタンパク質を抽出したものである。リンタンパク質を乳から抽出する方法としては、酸の添加により乳清から凝固抽出する方法（酸カゼイン）、あるいは、膜分離技術によりカゼインミセルを濃縮する方法（Ｍｉｌｋ　Ｐｒｏｔｅｉｎ　Ｃｏｎｃｅｎｔｒａｔｅ）などが挙げられる。このうち酸の添加により得られるリン蛋白の酸カゼインは、適度な粘性を持ち、カゼイングルーとして知られる天然系の接着剤組成物で用いられるが、この酸カゼインを用いることで、有機繊維と被覆ゴム組成物との接着性が向上する。 Here, the above-mentioned (B) casein is a phosphoprotein contained in a large amount in milk. In addition, the casein is an extract of a phosphoprotein that normally exists as casein micelles and is contained in milk. Examples of 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. Of these, 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.
　上記酸カゼインは、乳に酸を加えてｐＨ４．６とすると、カゼインに結合しているこれらの塩が離れてカゼインが等電沈殿してくる。この等電沈殿カゼイン（酸カゼイン）をアルカリに溶かすと、透明な可溶性のカゼイン塩の溶液が得られる。通常、本発明において使用されるカゼインまたはカゼイン塩は、粉末などの固体の形態、ペーストの形態、溶液、分散液または懸濁液の水性の形態で入手できるが、本発明の接着剤組成物への使用においては、溶液の状態で、特に、水溶液として使用することが好ましい。カゼインとして、乳由来の等電沈殿カゼインまたはそのアルカリ塩であって、固体、ペースト、溶液、分散液または懸濁液の形態であるものを用いることで、有機繊維と被覆ゴム組成物の接着性が、より良好となる。 When the acid casein is adjusted to pH 4.6 by adding an acid to milk, these salts bound to the casein are separated and the casein is isoelectrically precipitated. Dissolving this isoelectrically precipitated casein (acid casein) in an alkali gives a clear, soluble solution of casein salt. Usually, 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.
　本発明の一実施形態において、本発明の有機繊維用接着剤組成物が含有する上記（Ｂ）カゼインが示す作用の原理の一例を、図２および図３を参照しつつ、説明する。 In one embodiment of the present invention, an example of the principle of action of (B) casein contained in the adhesive composition for organic fibers of the present invention will be described with reference to FIGS. 2 and 3.
　従来、レゾルシンとホルムアルデヒドを含有する有機繊維用接着剤組成物では、これらレゾルシンとホルムアルデヒドが、水溶媒に分散するゴムラテックス粒子間でレゾール型レゾルシン・ホルムアルデヒド縮合物を形成するとともに、該有機繊維用接着剤組成物中のゴムラテックスの表面で、乳化剤として使用されるロジン酸塩等にレゾール型レゾルシン・ホルムアルデヒド縮合物のメチロール基が付加し共縮合して、これにより形成されたフェノール系樹脂の化学的な架橋による被覆によって、ゴムラテックスの粘着性が抑制されていた。 Conventionally, in an adhesive composition for organic fibers containing resorcin and formaldehyde, these resorcin and formaldehyde form a resole-type resorcin-formaldehyde condensate between rubber latex particles dispersed in an aqueous solvent, and the adhesive for the organic fiber is adhered. On the surface of the rubber latex in the agent composition, the methylol group of the resole-type resorcin / formaldehyde condensate is added to the rosinate used as an emulsifier and co-condensed, and the chemical of the phenolic resin formed thereby is chemically condensed. The adhesiveness of the rubber latex was suppressed by the coating by formaldehyde.
　一方、本発明の有機繊維用接着剤組成物においては、ゲル化温度以下でカゼイン１２同士が水中でネットワークを形成して、不飽和ジエンを有するゴムラテックス１１（コア）の表面を被覆する。不飽和ジエンを有するゴムラテックス１１は、表面に乳化したロジン酸塩のカルボン酸等によりマイナス（－）荷電を帯びており、これにカゼイン１２分子のアミノ基（－ＮＨ２）や、含まれる場合にはチオール基（－ＳＨ）等のカチオン性基が、静電的な引力で吸着して複合体となり、そして、この被覆によって、不飽和ジエンを有するゴムラテックス１１の粘着性が抑制される（ラテックス－カゼイン保護膜効果２０）（図２を参照）。 On the other hand, in the adhesive composition for organic fibers of the present invention, 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).
　この結果、（Ｂ）カゼインを含有する本発明の有機繊維用接着剤組成物は、接着剤液のせん断歪下での機械的安定性の指標として測定されるゴムラテックスの粘着性を抑制することによって、有機繊維コードを有機繊維用接着剤組成物で被覆して乾燥・熱硬化させる工程において、ロール等に対する該有機繊維用接着剤組成物の付着を抑制することが可能となり、作業性が良好なものとなる。 As a result, 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.
　また、有機繊維コード１の表面に被覆された本発明の有機繊維用接着剤組成物２中のカゼイン１２は、熱処理により反応性の高いロジン酸のカルボン酸部等とアミド結合またはエステル結合で化学架橋することなどで、有機繊維と被覆ゴム組成物の接着性が良好なものとなる。 Further, the 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. By cross-linking or the like, the adhesiveness between the organic fiber and the coated rubber composition becomes good.
　加えて、本発明の有機繊維用接着剤組成物が（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物を含む場合、カゼイン１２は、その有するアミノ基（－ＮＨ２）、水酸基（－ＯＨ）等が、乾燥後の高温熱処理によって、（熱解離性ブロックド）イソシアネート基を有する水性化合物によって形成されたウレタン樹脂１３が有する活性化イソシアネート基１４と、カゼイン－イソシアネート架橋２２を形成する（図３を参照）。この結果、（Ｂ）カゼインと（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物とを含有する接着剤組成物は、有機繊維と被覆ゴム組成物の接着性がより良好なものとなる。 In addition, when 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). As a result, 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.
　また、本発明の有機繊維用接着剤組成物が（Ｂ）カゼインを含むと、カゼイン１２がリンタンパク質であることから、カゼインのリン酸基を介したカゼインミセルを形成する特徴があり、（Ｂ）カゼイン同士が強固に架橋するなどの相互作用を生ずるので、有機繊維と被覆ゴム組成物との接着性がより良好なものとなる。 Further, when the adhesive composition for organic fibers of the present invention contains (B) casein, since 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.
　なお、酸カゼインは水と混合しただけでは溶解しないため、これにアルカリ性物質（水酸化ナトリウム、硼砂、アンモニアなど）を添加して撹拌していくと溶解する。また、熱を加えながら撹拌すると速く溶解する。カゼインは、熱による変性を受けにくいたんぱく質と言われており、８０℃前後で変性が始まるので、８０℃以下とすることが好ましい。酸カゼインは、水と懸濁した液でも、水に溶解した成分が前述のラテックス－カゼイン保護膜効果２０を有するため、本発明におけるラテックス粘着の抑制機能を奏するが、溶解しないカゼインの懸濁粒子があると、装置に粒子が付着するなどにより作業性が低下するため、完全に水溶した液状態として使用することが好ましい。 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.
　牛乳中の乳タンパク成分は、乳清とカゼインからなり、カゼインは乳中の成分のリン酸とともに、カルシウム－カゼイン－リン酸複合体の形で存在している。このカゼインは、脱脂乳をｐＨ４．６に調整し、沈殿させることで乳清と分離させることができる。このカゼインミセルは、酸で等電点沈殿した酸カゼインをアルカリで再溶解することで、牛乳中の乳清から分離して、工業レベルで製造される機能性タンパク質素材として、食品のみならず医薬品、化粧品の製造で広く用いられている。 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.
　また、牛乳中のカゼインミセルを膜分離して濃縮したＭｉｌｋ　Ｐｒｏｔｅｉｎ　Ｃｏｎｃｅｎｔｒａｔｅ（ＭＰＣ）などの乳素材は、酸カゼインと比較して単価が比較的高くなるが、カゼインとして用いることができる。 In addition, 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.
　さらに、乳中のカゼインミセルを形成する、リン酸イオンやカルシウムイオンなどを、酸カゼインやその塩に添加した水溶液を用いることができる。カルシウムリン酸複合体によるカゼイン分子間の架橋を強化すると、接着剤組成物からなる接着剤層の耐破壊抗力が向上し、ひいては接着力を向上する場合があるので、本発明の接着剤組成物には、これらのリン酸イオンやカルシウムイオンを供給する塩を添加することができる。 Furthermore, 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. When 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. Can be added with a salt that supplies these phosphate ions and calcium ions.
　本発明の有機繊維用接着剤組成物中の固形分全体に占める、上記（Ｂ）カゼインの含有量（固形分含有率）は、特に限定されるものではないが、０．１質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、０．８質量％以上であることがさらに好ましい。また、上記（Ｂ）カゼインの含有量は、１５質量％以下であることが好ましく、１０質量％以下であることがより好ましく、５質量％以下であることがさらに好ましい。上記（Ｂ）カゼインの含有量が、０．１質量％以上であれば、ロール等への該有機繊維用接着剤組成物の付着をより抑制することが可能となり、作業性がより良好となる利点があるからである。また、上記（Ｂ）カゼインの含有量が、１５質量％以下であれば、接着剤層に含まれるカゼイン量が多くなり過ぎず、接着剤層の耐破壊抗力を十分に確保することができるからである。 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. When 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.
＜（Ｃ），（Ｄ）および（Ｅ）＞
　本発明の有機繊維用接着剤組成物は、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物、および、（Ｅ）ポリフェノールからなる群から選択される１種以上の化合物を含む。 <(C), (D) and (E)>
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.
　本発明の有機繊維用接着剤組成物において、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、および、（Ｄ）エポキシド化合物は、架橋剤として機能して、有機繊維と被覆ゴム組成物との接着性の向上に寄与する。 In the adhesive composition for organic fibers of the present invention, (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.
　一方、（Ｅ）ポリフェノールは、接着剤組成物と有機繊維表面との親和性を向上させる機能を有し、その結果として、有機繊維と被覆ゴム組成物との接着性を向上させることができる。 On the other hand, (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.
　よって、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物、および、（Ｅ）ポリフェノールは、いずれも、有機繊維と被覆ゴム組成物との接着性の向上に寄与する。 Therefore, (C) an aqueous compound having a (heat dissociative blocked) isocyanate group, (D) an epoxide compound, and (E) polyphenol all improve the adhesiveness between the organic fiber and the coated rubber composition. Contribute.
＜（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物＞
　上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物の（熱解離性ブロックド）イソシアネート基とは、熱解離性ブロックドイソシアネート基またはイソシアネート基を意味する。具体的には、上記（熱解離性ブロックド）イソシアネート基とは、（イ）イソシアネート基が当該イソシアネート基に対する熱解離性ブロック剤と反応して生じた熱解離性ブロックドイソシアネート基、（ロ）イソシアネート基が当該イソシアネート基に対する熱解離性ブロック剤と未反応であるイソシアネート基、（ハ）熱解離性ブロックドイソシアネート基から熱解離性ブロック剤が解離して生じたイソシアネート基、および、（ニ）イソシアネート基、を含む。 <(C) (Thermal dissociative blocked) Aqueous compound having an isocyanate group>
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. Specifically, 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). An isocyanate group in which the isocyanate group has not reacted with the heat-dissociable blocking agent for the isocyanate group, (c) an isocyanate group generated by dissociating the heat-dissociable blocking agent from the heat-dissociable blocked isocyanate group, and (d). Contains isocyanate groups.
　上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物の水性とは、水溶性または水分散性であることを示す。また、上記水溶性とは、必ずしも完全な水溶性を意味するのではなく、部分的に水溶性であること、または、有機繊維用接着剤組成物の水溶液中で相分離をしないことをも意味する。 (C) 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.
　上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物は、（Ｃ－１）芳香環を有するポリイソシアネートと活性水素基を１個以上有するブロック剤との付加生成物からなる水分散性（熱解離性ブロックド）イソシアネート化合物（以下、単に「（Ｃ－１）成分」とも称する）であることが好ましい。この場合、有機繊維と被覆ゴム組成物の接着性が、より良好となる。 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.
　ここで、上記（Ｃ－１）成分に関して、活性水素基とは、好適な条件下に置いたとき、活性水素（原子状水素（水素ラジカル）および水素化物イオン（ヒドリド））となる水素を含む基のことを意味する。上記活性水素基の例としては、アミノ基、水酸基が挙げられる。 Here, with respect to the above component (C-1), 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. Examples of the active hydrogen group include an amino group and a hydroxyl group.
　上記熱解離性ブロック剤は、イソシアネート基を任意の化学反応から保護しつつ、必要に応じて熱処理をすることによりブロック剤を解離させて、イソシアネート基を復元することを可能とするブロック剤化合物であれば、特に限定されるものではない。具体的には、図１で示される工程で、接着処理液を付着・乾燥させた後における、熱硬化を行う加熱処理の温度において、熱解離性ブロック剤で封鎖されて反応性が抑えられたイソシアネート基の架橋反応性が回復できるような熱解離温度であることが好ましい。 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.
　ブロック剤としては、アルコール、フェノール、活性メチレン、オキシム、ラクタム、アミン等が挙げられ、特に限定されず、具体的には、ε－カプロラクタム、δ－バレロラクタム、γ－ブチロラクタム等のラクタム類；フェノール、クレゾール、エチルフェノール、ブチルフェノール、オクチルフェノール、ノニルフェノール、ジノニルフェノール、チオフェノール、クロルフェノール、アミルフェノール等のフェノール類；メチルエチルケトキシム、アセトキシム、アセトフェノンオキシム、ベンゾフェノンオキシム、シクロヘキサノンオキシム等のオキシム類；メタノール、エタノール、ブタノール、イソプロピルアルコール、ブチルアルコール、シクロヘキサノール等のアルコール類；ジメチルマロネート、ジエチルマロネート等のマロン酸ジアルキルエステル類；アセト酢酸メチル、アセト酢酸エチル、アセチルアセトン等の活性メチレン類、ブチルメルカプタン、ドデシルメルカプタン等のメルカプタン類；アセトアニリド、酢酸アミド等のアミド類；コハク酸イミド、フタル酸イミド、マレイン酸イミド等のイミド類；重亜硫酸ソーダ等の亜硫酸塩類；メチルセロソルブ、エチルセロソルブおよびブチルセロソルブ等のセロソルブ類；ピラゾール、３，５－ジメチルピラゾール、３－メチルピラゾール、４－ベンジル－３，５－ジメチルピラゾール、４－ニトロ－３，５－ジメチルピラゾール、４－ブロモ－３，５－ジメチルピラゾールおよび３－メチル－５－フェニルピラゾール等のピラゾール類；ジメチルアミン、ジエチルアミン、ジ－ｎ－プロピルアミン、ジイソプロピルアミン、ジシクロヘキシルアミン、ジフェニルアミン、キシリジン、Ｎ，Ｎ－ジエチルヒドロキシアミン、Ｎ，Ｎ’－ジフェニルホルムアミジン、２－ヒドロキシピリジン、３－ヒドロキシピリジンおよび２－メルカプトピリジン等のアミン類：および、１，２，４－トリアゾール等のトリアゾール類などが挙げられる。これらの２種以上の混合物等を使用してもよい。 Examples of the blocking agent include alcohol, phenol, active methylene, oxime, lactam, amine and the like, and are not particularly limited, and specifically, lactams such as ε-caprolactam, δ-valerolactam and γ-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; imides such as succinic acid imide, phthalate imide and maleic acid imide; sulfites such as sodium bisulfite; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; Pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole and 3-methyl Pyrazoles such as -5-phenylpyrazole; dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dicyclohexylamine, diphenylamine, xylidine, N, N-diethylhydroxyamine, N, N'-diphenylform amidine, 2 -Amines such as hydroxypyridine, 3-hydroxypyridine and 2-mercaptopyridine: and triazoles such as 1,2,4-triazole and the like. A mixture of two or more of these may be used.
　これらのブロック剤のうちでも、加熱での熱解離による接着剤組成物の熱硬化が安定して得られ易いフェノール、ε－カプロラクタムおよびケトオキシムを好適に用いることができる。 Among these blocking agents, phenol, ε-caprolactam and ketooxime, which can be easily obtained by stably heat-curing the adhesive composition by thermal dissociation by heating, can be preferably used.
　また、上記（Ｃ－１）成分は、具体的には、芳香族ポリイソシアネート類または芳香脂肪族ポリイソシアネート類を含み、芳香族イソシアネート類としては、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート等のフェニレンジイソシアネート類；２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート（ＴＤＩ）等のトリレンジイソシアネート類；２，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート等のジフェニルメタンジイソシアネート類；ポリメチレンポリフェニルポリイソシアネート（ポリメリックＭＤＩ）；ｍ－またはｐ－イソシアナトフェニルスルホニルイソシアネート類；４，４’－ジイソシアナトビフェニル、３，３’－ジメチル－４，４’－ジイソシアナトビフェニル等のジイソシアナトビフェニル類；１，５－ナフチレンジイソシアネート等のナフタレンジイソシアネート類；等が挙げられる。芳香脂肪族ポリイソシアネート類としては、ｍ－キシリレンジイソシアネート、ｐ－キシリレンジイソシアネート（ＸＤＩ）、テトラメチルキシリレンジイソシアネート等のキシリレンジイソシアネート類；ジエチルベンゼンジイソシアネート；および、α，α，α，α－テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）；等が挙げられる。また、上記ポリイソシアネートのカルボジイミド、ポリオールおよびアロファネート等の変性物等が挙げられる。 Further, 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; 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 diisocyanate; and the like. Examples of aromatic aliphatic polyisocyanates include xylylene diisocyanates such as m-xylylene diisocyanate, p-xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate; diethylbenzene diisocyanate; and α, α, α, α-tetra. Methylxylylene diisocyanate (TMXDI); and the like. In addition, modified products such as carbodiimide, polyol and allophanate of the polyisocyanate can be mentioned.
　これらの芳香環を分子内に含むポリイソシアネートのうち、接着剤組成物のコード集束性の観点から、芳香族イソシアネートが好ましく、より好ましくは、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）あるいはポリメチレンポリフェニルポリイソシアネート（ポリメリックＭＤＩ）であり、特に好ましくは、ジフェニルメタンジイソシアネート（ＭＤＩ）類である。（Ｃ－１）成分として、メチレンジフェニルイソシアネート類のブロック体、中でも、メチレンジフェニルジイソシアネート（ジフェニルメタンジイソシアネート）のブロック体を用いることで、有機繊維と被覆ゴム組成物の接着性が、より良好となる。 Of the polyisocyanates containing these aromatic rings in the molecule, 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), particularly preferably diphenylmethane diisocyanate (MDI). By using 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.
　また、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物は、（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物（以下、単に「（Ｃ－２）成分」とも称する）であることが、より好ましい。この場合も、有機繊維と被覆ゴム組成物の接着性が、より良好となる。上記（Ｃ－２）成分の詳細については、説明の便宜上、後述する。 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. The details of the above component (C-2) will be described later for convenience of explanation.
　本発明の有機繊維用接着剤組成物の固形分全体に占める、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物の含有量（固形分含有率）は、特に限定はされるものではないが、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、２０質量％以上であることがさらに好ましい。また、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物の含有量は、７５質量％以下であることが好ましく、６０質量％以下であることがより好ましく、４５質量％以下であることがさらに好ましい。上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物の含有量が、５質量％以上であれば、有機繊維と被覆ゴム組成物の接着性がより良好なものになるからである。また、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物の含有量が、７５質量％以下であれば、有機繊維用接着剤組成物に配合するゴムラテックス等の他の成分の量を、相対して一定以上確保することが可能となり、その結果、被着ゴムとの接着性がより良好となるからである。 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. This is because when the content of the aqueous compound having the (heat dissociative blocked) isocyanate group (C) is 5% by mass or more, the adhesiveness between the organic fiber and the coated rubber composition becomes better. .. Further, when the content of the aqueous compound having the (C) (heat dissociable blocked) isocyanate group is 75% by mass or less, other components such as rubber latex to be blended in the adhesive composition for organic fibers may be used. This is because it is possible to secure a certain amount or more relative to each other, and as a result, the adhesiveness with the adherend rubber becomes better.
　ここで、従来の、レゾルシンとホルムアルデヒドを含有する有機繊維用接着剤組成物では、これらレゾルシンとホルムアルデヒドが共縮合したフェノール系樹脂（海に例えられる）中にゴムラテックス粒子（島に例えられる）が分散した海島構造が形成され、これにより、有機繊維表面を被覆するフェノール系樹脂と有機繊維との間の良好な接着性を得ていた。 Here, in the conventional adhesive composition for organic fibers containing resorcin and formaldehyde, rubber latex particles (compared to an island) are contained in a phenolic resin (compared to the sea) in which these resorcin and formaldehyde are co-condensed. A dispersed sea-island structure was formed, which provided good adhesion between the phenolic resin covering the surface of the organic fiber and the organic fiber.
　一方、本発明の有機繊維用接着剤組成物の一好適実施態様においては、上記レゾルシンとホルムアルデヒドが共縮合したフェノール系樹脂に代わり、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物が、以下の２つの機能効果（ａ），（ｂ）をもって、接着促進剤として作用する。これらの結果、上記有機繊維用接着剤組成物においては、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物が、有機繊維と被覆ゴム組成物の接着性が良好という特徴に寄与する。 On the other hand, in one preferred embodiment of the adhesive composition for organic fibers of the present invention, 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). As a result, in the above-mentioned adhesive composition for organic fibers, 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.
　（ａ）有機繊維と有機繊維用接着剤組成物による接着剤層との界面近傍の位置に、上記水性化合物が分布して、上記有機繊維と上記接着剤層との接着を促進する機能効果。
　（ｂ）有機繊維用接着剤組成物による接着剤層内で、上記（熱解離性ブロックド）イソシアネート基を有する化合物によるイソシアネート基による架橋で３次元ネットワーク構造が形成され、上記接着剤層を補強する機能効果。 (A) A functional effect in which the aqueous compound is distributed at a position near the interface between the organic fiber and the adhesive layer of the adhesive composition for organic fiber to promote the adhesion between the organic fiber and the adhesive layer.
(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. Functional effect.
　本発明の有機繊維用接着剤組成物の一実施形態において、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物の上記２つの接着促進剤としての機能効果（ａ），（ｂ）の原理の一例について、以下、詳細に説明する。 In one embodiment of the adhesive composition for organic fibers of the present invention, 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. An example of the principle of)) will be described in detail below.
　具体的には、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物が（Ｃ－１）成分である場合については、図２も参照しながら、また、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物が（Ｃ－２）成分である場合については、図３も参照しながら、それぞれ説明する。 Specifically, when 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）の接着促進剤としての機能効果について＞＞
　有機繊維コードとして汎用されるポリエチレンテレフタレート等のポリエステルの合成樹脂素材は、扁平線状の高分子鎖からなる。そして、該高分子鎖の表面または該高分子鎖の間隙は、該高分子鎖に含まれる芳香環等に由来するπ電子的雰囲気を有している。さらに、ポリエステルは、６，６－ナイロンに比べて、表面の水酸基が特に少ない。そこで、従来より、ポリエステルからなる有機繊維コードに対して使用される有機繊維用接着剤組成物は、十分な接着力を得るために、上記有機繊維用接着剤組成物が有機繊維の高分子鎖の間隙へ分散すること、および、上記有機繊維用接着剤組成物による接着剤層が上記有機繊維の高分子鎖の表面に密着すること、を目的として、芳香族性π電子を有する芳香環を側面に有する平面的な構造（有機繊維に拡散しやすい部分）の分子を、接着促進剤として含有してきた。 << About the functional effect of (a) as an adhesion promoter >>
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 π-electronic atmosphere derived from the aromatic ring or the like contained in the polymer chain. Furthermore, 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 π 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.
　そのような接着促進剤の具体例としては、従来より、上記（Ｃ－１）成分が使用されてきている。 As a specific example of such an adhesion promoter, the above component (C-1) has been conventionally used.
　上記（Ｃ－１）成分としては、粒子径が０．０１～０．５０μｍであるメチレンジフェニルジイソシアネート等の（ブロックド）イソシアネート（特許文献３参照）であることが好ましい。 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 μm.
　当該（Ｃ－１）成分を含む接着剤層においては、図２に示すように、有機繊維用接着剤組成物２による接着剤層３２内で、（Ｃ－１）成分４０が、有機繊維コード１に拡散しつつ（芳香族イソシアネート－有機繊維拡散効果４１）、接着剤層に含まれるカゼイン１２と共有結合によるカゼイン－イソシアネート架橋２２を形成することで、有機繊維用接着剤組成物２が有機繊維コード１の高分子鎖の間隙へ分散するとともに、有機繊維用接着剤組成物２による接着剤層３２が上記有機繊維コード１の高分子鎖の表面に密着することとなる。 In the adhesive layer containing the component (C-1), as shown in FIG. 2, 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.
　なお、上記（Ｃ－１）成分の粒子径は、前述の通り、０．０１～０．５０μｍであることが好ましい。上記（Ｃ－１）成分の粒子径が０．０１μｍ未満であると、時間の経過とともに上記（Ｃ－１）成分が、接着剤層中で、有機繊維の高分子鎖の表面から、芳香族性π電子がより豊富に存在する有機繊維の高分子鎖の間隙へと拡散しやすいという性質があり、これに伴い接着促進剤としての効果が低下していく。そのため、有機繊維の表面に残留するためには、上記（Ｃ－１）成分の粒径がある程度大きいことが必要であるためである。また、上記（Ｃ－１）成分の粒径が０．５０μｍ以下の場合、粒径が小さいほど、該（Ｃ－１）成分が液中で沈降し難く、接着剤層での分散が不均一になりにくいためである。 The particle size of the component (C-1) is preferably 0.01 to 0.50 μm as described above. When the particle size of the component (C-1) is less than 0.01 μm, 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 π 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. Further, when the particle size of the component (C-1) is 0.50 μm 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.
　また、上記有機繊維用接着剤組成物は、分子構造内に、有機繊維に拡散しやすい部分である疎水性の芳香族ポリイソシアネート部に加えて、有機繊維に拡散しがたい部分である親水性の分子鎖部も有する、（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物を含むことが、さらに好ましい。 Further, in the above-mentioned adhesive composition for organic fibers, in addition to the hydrophobic aromatic polyisocyanate portion which is a portion which easily diffuses into the organic fiber in the molecular structure, 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.
　図３に示すように、有機繊維用接着剤組成物２による接着剤層３２内で、上記（Ｃ－２）成分によって形成されたウレタン樹脂１３は、有機繊維コード１との相互作用を得やすい部分１５と、有機繊維コード１に拡散しがたい部分１６との両方を有する。 As shown in FIG. 3, 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.
　このうち、有機繊維コードとの相互作用を得やすい部分１５の存在により、有機繊維用接着剤組成物２による接着剤層３２が、上記有機繊維コード１の高分子鎖の表面に密着することとなる。また、有機繊維コード１に拡散しがたい部分１６の存在により、上記（Ｃ－２）成分によって形成されたウレタン樹脂１３は、接着剤層３２との界面で接着性を促進する機能効果が持続することとなる（水性ウレタン－有機繊維界面効果２４）。 Of these, 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. Become. Further, due to the presence of the portion 16 that is difficult to diffuse in 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).
　これらの結果、上記（Ｃ－２）成分を含有する有機繊維用接着剤組成物は、有機繊維コードと被覆ゴム組成物の接着性が良好なものとなる。 As a result, 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.
　なお、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物は、アニオン性あるいはノニオン性の水溶性官能基を有する芳香族ポリイソシアネート化合物であると、疎水性の有機繊維コード１の表面より水中に分散する傾向があるため、上記（Ｃ－２）成分であることがより好ましい。 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.
＜＜（ｂ）の接着促進剤としての機能効果について＞＞
　上記（Ｃ－１）成分を含む接着剤層では、図２で示すように、該（Ｃ－１）成分４０のブロック剤が熱解離した活性化イソシアネート基が、隣接するカゼイン１２の分子鎖と、カゼイン－イソシアネート架橋２２を形成し、３次元ネットワーク構造を含む接着剤層が得られる。この結果、上記（Ｃ－１）成分を含有する有機繊維用接着剤組成物は、有機繊維コードと被覆ゴム組成物の接着性が良好なものとなる。 << About the functional effect of (b) as an adhesion promoter >>
In the adhesive layer containing the component (C-1), as shown in FIG. 2, the activated isocyanate group in which the blocking agent of the component (C-1) 40 is thermally dissociated is combined with the adjacent molecular chain of casein 12. , Casein-isocyanate bridge 22 is formed, and an adhesive layer containing a three-dimensional network structure is obtained. As a result, the adhesive composition for organic fibers containing the component (C-1) has good adhesiveness between the organic fiber cord and the coated rubber composition.
　なお、芳香族を主体とする粉体を強制的に乳化して分散させた材料を使うため、該化合物が液中で沈降して、接着剤層での分散が不均一になり凝集したりしないように、図１の浸漬用浴槽（ディッピング槽）３は、攪拌することが好ましい。 Since a material in which powder mainly composed of aromatics is forcibly emulsified and dispersed is used, the compound does not settle in the liquid and disperse in the adhesive layer becomes non-uniform and does not aggregate. As described above, it is preferable that the dipping bath (dipping tank) 3 of FIG. 1 is stirred.
　一方、本発明の有機繊維用接着剤組成物では、上記（Ｃ－２）成分が接着促進剤として含有されることがより好ましい。そして、上記（Ｃ－２）成分は、その分子内にアルキレンオキサイド部等を含有するので、水が膨潤することによる自己乳化等で、水中に均一に分散させることができる。 On the other hand, in the adhesive composition for organic fibers of the present invention, it is more preferable that 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.
　さらに、水中に均一に分散した上記（Ｃ－２）成分が、その分子内に疎水性の有機イソシアネート部位を含有するために、例えば、会合型シックナーで使用する水溶性ウレタンと同様に、隣り合う水溶性ウレタンの疎水性部同士で安定な会合ミセルを形成し、液中で均一分散した水性ウレタン間の疎水性相互作用による３次元ネットワーク構造を持つようになる。 Further, since 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.
　次に、上記疎水結合による３次元ネットワーク構造を持つ有機繊維用接着剤組成物を有機繊維に被覆した後、乾燥、熱硬化させる。すると、図３で示すように、ブロック剤が熱解離した活性化イソシアネート基１４が、隣接するもの同士で、共有結合による活性化イソシアネート架橋２３を形成し、上記（Ｃ－２）成分によって形成されたウレタン樹脂１３の３次元ネットワーク構造を含む接着剤層が得られる。その結果、上記（Ｃ－２）成分を含有する有機繊維用接着剤組成物によれば、有機繊維と被覆ゴム組成物の接着性が良好なものとなる。 Next, 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. As a result, according to the adhesive composition for organic fibers containing the component (C-2), the adhesiveness between the organic fibers and the coated rubber composition is good.
＜＜熱解離性ブロック剤、水性ウレタン化合物＞＞
　上記（Ｃ－２）成分の熱解離性ブロック剤は、イソシアネート基を任意の化学反応から保護しつつ、必要に応じて熱処理をすることによりブロック剤を解離させて、イソシアネート基を復元することが可能であるようなブロック剤化合物であれば、特に限定されるものではない。上記熱解離性ブロック剤の具体例としては、上記（Ｃ－１）成分について前述したブロック剤と同じ化合物を用いることができ、好ましくは、フェノール、チオフェノール、クロルフェノール、クレゾール、レゾルシノール、ｐ－ｓｅｃ－ブチルフェノール、ｐ－ｔｅｒｔ－ブチルフェノール、ｐ－ｓｅｃ－アミルフェノール、ｐ－オクチルフェノール、ｐ－ノニルフェノール等のフェノール類；イソプロピルアルコール、ｔｅｒｔ－ブチルアルコール等の第２級または第３級のアルコール；ジフェニルアミン、キシリジン等の芳香族第２級アミン類；フタル酸イミド類；δ－バレロラクタム等のラクタム類；ε－カプロラクタム等のカプロラクタム類；ジエチルマロネート、ジメチルマロネートなどのマロン酸ジアルキルエステル、アセチルアセトン、アセト酢酸アルキルエステル等の活性メチレン化合物；アセトキシム、メチルエチルケトキシム、シクロヘキサノンオキシム等のオキシム類；３－ヒドロキシピリジン、１，２－ピラゾール、３，５－ジメチルピラゾール、１，２，４－トリアゾール、ジイソプロピルアミン、Ｎ，Ｎ’－ジフェニルホルムアミジン等の塩基性窒素化合物および酸性亜硫酸ソーダ等が挙げられる。 << Thermal dissociative blocking agent, aqueous urethane compound >>
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. As a specific example of the heat-dissociable blocking agent, 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 δ-valerolactam; caprolactams such as ε-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 acetoxime, methylethylketoxim, cyclohexanone oxime; 3-hydroxypyridine, 1,2-pyrazole, 3,5-dimethylpyrazole, 1,2,4-triazole, diisopropylamine, Examples thereof include basic nitrogen compounds such as N, N'-diphenylformamidine and acidic sodium sulfite.
　これらのブロック剤の中でも、加熱での熱解離による接着剤組成物の熱硬化が安定して得られ易いフェノール、ε－カプロラクタムおよびケトオキシムを好適に用いることができる。 Among these blocking agents, phenol, ε-caprolactam and ketooxime, which can be easily obtained by stably heat-curing the adhesive composition by thermal dissociation by heating, can be preferably used.
　ここで、上記水性ウレタン化合物の水性とは、水溶性または水分散性であることを意味する。また、上記水溶性とは、必ずしも完全な水溶性を意味するのではなく、部分的に水溶性であること、または、有機繊維用接着剤組成物の水溶液中で相分離をしないことをも意味する。 Here, 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.
　上記水性ウレタン化合物のウレタン化合物は、アミンの窒素とカルボニル基の炭素の間で形成された共有結合を有する化合物であり、下記一般式（２）で表される化合物を意味する。　
Figure JPOXMLDOC01-appb-I000002
　上記式（２）中、Ｒ、Ｒ’は、炭化水素基を表す。 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).
Figure JPOXMLDOC01-appb-I000002
In the above formula (2), R and R'represent a hydrocarbon group.
　上記（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物の分子量は、水性を保てるものであれば特に限定されるものではなく、好ましくは数平均分子量１，５００～１００，０００であり、特に好ましくは数平均分子量９，０００以下である。 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.
　上記（Ｃ－２）成分を合成する方法は、前述の通り、特に限定されるものではなく、特開昭６３－５１４７４号公報に記載の方法等、公知の方法とすることができる。 As described above, 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.
＜＜（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物の好ましい実施態様＞＞
　上記（Ｃ－２）成分の好ましい実施態様は、（α）３個以上、５個以下の官能基を有する数平均分子量が２，０００以下の有機ポリイソシアネート化合物、（β）２個以上、４個以下の活性水素基を有する数平均分子量が５，０００以下の化合物、（γ）熱解離性ブロック剤、および、（δ）少なくとも１つの活性水素基と、アニオン性、カチオン性または非イオン性である少なくとも１つの親水基と、を有する化合物を、所定の混合比率になるように混合して、反応させた後の反応生成物であって、かつ、イソシアネート基（－ＮＣＯ）の分子量を４２としたときの、上記反応生成物中における（熱解離性ブロックド）イソシアネート基の構成比率が、０．５質量％以上、１１質量％以下であることを特徴とする。この場合、有機繊維と被覆ゴム組成物の接着性が、より良好となる。このような（Ｃ－２）成分は、（熱解離性ブロックド）イソシアネート基からなる部位と、親水性基を有する親水性の部位を併せ持つために、ウレタン化合物の自己水溶性が高まる利点を有するからである。 << (C-2) (Preferable Embodiment of an aqueous urethane compound having a (heat dissociative blocked) isocyanate group >>
A preferred embodiment of the component (C-2) is an organic polyisocyanate compound having (α) 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less, and (β) 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, (γ) a thermally dissociable blocking agent, and (δ) at least one active hydrogen group. It is a reaction product after mixing and reacting a compound having at least one hydrophilic group and having a predetermined mixing ratio so as to have a predetermined mixing ratio, and the molecular weight of the isocyanate group (-NCO) is 42. 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.
　（α）、（β）、（γ）および（δ）の総和量に対するそれぞれの混合比率は、（α）については、４０質量％以上、８５質量％以下、（β）については、５質量％以上、３５質量％以下、（γ）については、５質量％以上、３５質量％以下、また、（δ）については、５質量％以上、３５質量％以下である。 The mixing ratios of (α), (β), (γ) and (δ) to the total amount were 40% by mass or more and 85% by mass or less for (α), and 5% by mass for (β). As mentioned above, 35% by mass or less, (γ) is 5% by mass or more and 35% by mass or less, and (δ) is 5% by mass or more and 35% by mass or less.
　上記（α）３個以上、５個以下の官能基を有する数平均分子量２，０００以下の有機ポリイソシアネート化合物は、特に限定されるものではないが、芳香族ポリイソシアネート化合物およびそのオリゴマーであることが好ましく、その他の脂肪族、脂環式、複素環式のポリイソシアネート化合物およびそのオリゴマーであってもよい。このような（α）３個以上、５個以下の官能基を有する数平均分子量２，０００以下の有機ポリイソシアネート化合物を反応させた後の反応生成物である（Ｃ－２）成分は、有機繊維の高分子鎖の間隙に、より分散しやすくなるからである。 The organic polyisocyanate compound having a number average molecular weight of 2,000 or less having (α) 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 (α) 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.
　具体例として、脂肪族ポリイソシアネート化合物としては、エチレンジイソシアネート、１，４－テトラメチレンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、１，１２－ドデカンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、リジンジイソシアネート等が挙げられ、脂環式ポリイソシアネート化合物としては、シクロブタン－１，３－ジイソシアネート、シクロヘキサン－１，３－ジイソシアネート、シクロヘキサン－１，４－ジイソシアネート、イソホロンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、メチルシクロヘキサン－２，４－ジイソシアネート、メチルシクロヘキサン－２，６－ジイソシアネート、１，３－（イソシアナトメチル）シクロヘキサン等が挙げられ、複素環式ポリイソシアネート化合物としては、１，３，５－トリス（２’－ヒドロキシエチル）イソシアヌル酸のトリレンジイソシアネート付加物等が挙げられ、芳香族ポリイソシアネート化合物としては、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ｍ－キシリレンジイソシアネート、ｐ－キシリレンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、ｍ－テトラメチルキシリレンジイソシアネート、ｐ－テトラメチルキシリレンジイソシアネート、メチントリス（４－フェニルイソシアネート）、トリス（４－イソシアナトフェニル）メタン、チオリン酸トリス（４－イソシアナトフェニルエステル）、３－イソプロペニル－α’，α’－ジメチルベンジルイソシアネートおよびこれらのオリゴマー混合物、または、これらのポリイソシアネート化合物のカルボジイミド、ポリオールおよびアロファネート等の変性物等が挙げられる。 As a specific example, as the 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, and 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-diisocyanate, 1,3- (isocyanatomethyl) cyclohexane and the like. Examples of the heterocyclic polyisocyanate compound 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 α', α'-dimethylbenzyl isocyanate and a mixture thereof, or modified products of these polyisocyanate compounds such as carbodiimide, polyol and allophanate.
　これらの中でも、芳香族ポリイソシアネート化合物が好ましく、特に好ましくは、メチレンジフェニルポリイソシアネート、ポリフェニレンポリメチレンポリイソシアネート等が挙げられる。特には、数平均分子量２，０００以下のポリフェニレンポリメチレンポリイソシアネートが好ましく、数平均分子量１，０００以下のポリフェニレンポリメチレンポリイソシアネートが特に好ましい。このような（α）３個以上、５個以下の官能基を有する数平均分子量２，０００以下の有機ポリイソシアネート化合物を反応させた後の反応生成物である（Ｃ－２）成分は、有機繊維の高分子鎖の間隙に、より分散しやすくなるからである。 Among these, aromatic polyisocyanate compounds are preferable, and methylenediphenyl polyisocyanate, polyphenylene polymethylene polyisocyanate and the like are particularly preferable. In particular, 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 component (C-2), which is a reaction product after reacting such an organic polyisocyanate compound having (α) 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.
　上記（β）２個以上、４個以下の活性水素基を有する数平均分子量５，０００以下の化合物としては、特に限定されるものではないが、具体的には、下記（ｉ）から（ｖｉｉ）よりなる群から選ばれる化合物等が挙げられる。
　（ｉ）２個以上４個以下の水酸基を有する数平均分子量５，０００以下の多価アルコール類、
　（ｉｉ）２個以上４個以下の第一級および／または第二級アミノ基を有する数平均分子量５，０００以下の多価アミン類、
　（ｉｉｉ）２個以上４個以下の第一級および／または第二級アミノ基と水酸基を有する数平均分子量５，０００以下のアミノアルコール類、
　（ｉｖ）２個以上４個以下の水酸基を有する数平均分子量５，０００以下のポリエステルポリオール類、
　（ｖ）２個以上４個以下の水酸基を有する数平均分子量５，０００以下のポリブタジエンポリオール類およびそれらと他のビニルモノマーとの共重合体、
　（ｖｉ）２個以上４個以下の水酸基を有する数平均分子量５，０００以下のポリクロロプレンポリオール類およびそれらと他のビニルモノマーとの共重合体、
　（ｖｉｉ）２個以上４個以下の水酸基を有する数平均分子量５，０００以下のポリエーテルポリオール類である、
　多価アミン、多価フェノールおよびアミノアルコール類のＣ２～Ｃ４のアルキレンオキサイド重付加物、Ｃ３以上の多価アルコール類のＣ２～Ｃ４のアルキレンオキサイド重付加物、Ｃ２～Ｃ４のアルキレンオキサイド共重合物、または、Ｃ３～Ｃ４のアルキレンオキサイド重合物。 The compound having (β) 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.
(I) Multihydric alcohols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
(Ii) Multivalent amines having a number average molecular weight of 5,000 or less and having 2 or more and 4 or less primary and / or secondary amino groups.
(Iii) Amino alcohols having a number average molecular weight of 5,000 or less and having 2 or more and 4 or less primary and / or secondary amino groups and hydroxyl groups.
(Iv) Polyester polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less,
(V) Polybutadiene polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less, and copolymers thereof with other vinyl monomers.
(Vi) Polychloroprene polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less, and copolymers thereof with other vinyl monomers.
(Vii) Polyester polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
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.
　ここで、上記（Ｃ－２）成分に関して、活性水素基とは、好適な条件下に置いたとき、活性水素（原子状水素（水素ラジカル）および水素化物イオン（ヒドリド））となる水素を含む基を意味する。上記活性水素基の例としては、アミノ基、水酸基が挙げられる。 Here, with respect to the above component (C-2), the active hydrogen group includes hydrogen that becomes active hydrogen (atomic hydrogen (hydrogen radical) and hydride ion (hydride)) when placed under suitable conditions. Means radical. Examples of the active hydrogen group include an amino group and a hydroxyl group.
　上記（δ）少なくとも１つの活性水素基と、アニオン性、カチオン性または非イオン性の少なくとも１つの親水基と、を有する化合物の、少なくとも１つの活性水素基とアニオン性の少なくとも１つの親水基とを有する化合物としては、特に限定されるものではないが、タウリン、Ｎ－メチルタウリン、Ｎ－ブチルタウリン、スルファニル酸等のアミノスルホン酸類、グリシン、アラニン等のアミノカルボン酸類等が挙げられる。 (Δ) 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. The compound having the above is 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.
　上記（α）、（β）、（γ）および（δ）を混合して反応させることにより、上記（Ｃ－２）成分を合成する方法は、特に限定されるものではないが、特開昭６３－５１４７４号公報に記載の方法等、公知の方法とすることができる。 The method for synthesizing the component (C-2) by mixing and reacting the above (α), (β), (γ) and (δ) 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）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物の別の好ましい実施態様＞＞
　上記（Ｃ－２）成分の別の好ましい実施態様は、（α）３個以上、５個以下の官能基を有する数平均分子量２，０００以下の有機ポリイソシアネート化合物、（β）２個以上、４個以下の活性水素基を有する数平均分子量５，０００以下の化合物、（γ）熱解離性ブロック剤、（δ）少なくとも１つの活性水素基と、アニオン性、カチオン性または非イオン性の少なくとも１つの親水基と、を有する化合物、および、（ε）活性水素基を含む、（α）、（β）、（γ）および（δ）以外の化合物とを、所定の混合比率となるように混合して、反応させた後の反応生成物であって、かつ、イソシアネート基（－ＮＣＯ）の分子量を４２としたときの、上記反応生成物中における（熱解離性ブロックド）イソシアネート基の構成比率が、０．５質量％以上、１１質量％以下であることを特徴とする。このような（Ｃ－２）成分は、（熱解離性ブロックド）イソシアネート基からなる部位と、親水性基を有する親水性の部位を併せ持つために、ウレタン化合物の自己水溶性が高まる利点を有するからである。 << (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 (α) 3 or more and 5 or less functional groups and having a number average molecular weight of 2,000 or less, and (β) 2 or more. A compound having 4 or less active hydrogen groups and having a number average molecular weight of 5,000 or less, (γ) a thermally dissociable blocking agent, (δ) at least one active hydrogen group, and at least anionic, cationic or nonionic. A compound having one hydrophilic group and a compound other than (α), (β), (γ) and (δ) containing a (ε) 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.
　（α）、（β）、（γ）、（δ）および（ε）の総和量に対するそれぞれの混合比率は、（α）については、４０質量％以上、８５質量％未満、（β）については、５質量％以上、３５質量％以下、（γ）については、５質量％以上、３５質量％以下、（δ）については、５質量％以上、３５質量％以下、（ε）については、０質量％より多く、４５質量％以下である。 The mixing ratios of (α), (β), (γ), (δ) and (ε) to the total amount are 40% by mass or more for (α), less than 85% by mass, and (β). 5% by mass or more, 35% by mass or less, 5% by mass or more for (γ), 35% by mass or less, 5% by mass or more for (δ), 35% by mass or less, 0 for (ε) More than mass% and less than 45% by mass.
　ここで、（α）３個以上、５個以下の官能基を有する数平均分子量２，０００以下の有機ポリイソシアネート化合物、（β）２個以上、４個以下の活性水素基を有する数平均分子量５，０００以下の化合物、（γ）熱解離性ブロック剤、および、（δ）少なくとも１つの活性水素基と、アニオン性、カチオン性または非イオン性の少なくとも１つの親水基と、を有する化合物は、混合比率以外、前述の＜＜（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物の好ましい実施態様＞＞に記載した通りである。 Here, (α) 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 (β) a number average molecular weight having 2 or more and 4 or less active hydrogen groups. Compounds having up to 5,000 compounds, (γ) thermally dissociable blocking agents, and (δ) at least one active hydrogen group and at least one anionic, cationic or nonionic hydrophilic group Other than the mixing ratio, it is as described in << (C-2) (Preferable Embodiment of Aqueous Urethane Compound Having a (Thermal Dissociable Blocked) Isocyanate Group >>> described above.
　上記（α）、（β）、（γ）、（δ）および（ε）を混合して反応させることにより、上記（Ｃ－２）成分を合成する方法は、特に限定されるものではないが、特開昭６３－５１４７４号公報に記載の方法等、公知の方法とすることができる。 The method for synthesizing the component (C-2) by mixing and reacting the above (α), (β), (γ), (δ) and (ε) is not particularly limited. , A known method such as the method described in JP-A-63-51474.
＜＜（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物のさらに別の好ましい実施態様＞＞
　上記（Ｃ－２）成分のさらに別の好ましい実施態様は、下記一般式（１）：
Figure JPOXMLDOC01-appb-I000003
［式（１）中、
　Ａは、有機ポリイソシアネート化合物の、活性水素基が脱離した残基、
　Ｘは、２個以上、４個以下の水酸基を有する、数平均分子量が５，０００以下のポリオール化合物の、活性水素基が脱離した残基、
　Ｙは、熱解離性ブロック剤の、活性水素基が脱離した残基、
　Ｚは、少なくとも１個の活性水素基と、少なくとも１個の塩を生成する基または親水性ポリエーテル鎖と、を有する化合物の、活性水素基が脱離した残基、
　ｎは、２以上４以下の整数、
　ｐ＋ｍは、２以上４以下の整数（ｍ≧０．２５）
を表す］で表されることを特徴とする。この場合も、有機繊維と被覆ゴム組成物の接着性が、より良好となる。上記（Ｃ－２）成分は、（熱解離性ブロックド）イソシアネート基からなる部位と、親水性基を有する親水性の部位を併せ持つために、ウレタン化合物の自己水溶性が高まる利点を有するからである。 << (C-2) (Thermal Dissociative Blocked) Yet Another Preferred Embodiment of an Aqueous Urethane Compound Having an Isocyanate Group >>
Yet another preferred embodiment of the above component (C-2) is the following general formula (1) :.
Figure JPOXMLDOC01-appb-I000003
[In equation (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]. In this case as well, the adhesiveness between the organic fiber and the coated rubber composition becomes better. This is because 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.
　ここで、一般式（１）中のＡである、有機ポリイソシアネート化合物の活性水素基が脱離した残基の、有機ポリイソシアネート化合物は、芳香族環を含むことが好ましい。（Ｃ－２）成分が有機繊維の高分子鎖の間隙に、より分散しやすくなるからである。 Here, it is preferable that 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.
　特に限定されるものではないが、具体的には例えば、メチレンジフェニルポリイソシアネート、ポリフェニレンポリメチレンポリイソシアネート等が挙げられる。数平均分子量６，０００以下のポリフェニレンポリメチレンポリイソシアネートが好ましく、数平均分子量４，０００以下であるポリフェニレンポリメチレンポリイソシアネートが特に好ましい。 Although not particularly limited, specific examples thereof include methylenediphenylpolyisocyanate and polyphenylenepolymethylenepolyisocyanate. Polyphenylene polymethylene polyisocyanate having a number average molecular weight of 6,000 or less is preferable, and polyphenylene polymethylene polyisocyanate having a number average molecular weight of 4,000 or less is particularly preferable.
　一般式（１）中のＸである、２個以上、４個以下の水酸基を有する数平均分子量が５，０００以下のポリオール化合物の活性水素基が脱離した残基の、２個以上、４個以下の水酸基を有する数平均分子量が５，０００以下のポリオール化合物としては、特に限定されるものではないが、具体的には、下記（ｉ）から（ｖｉ）よりなる群から選ばれる化合物等が挙げられる。
　（ｉ）２個以上４個以下の水酸基を有する、数平均分子量５，０００以下の多価アルコール類、
　（ｉｉ）２個以上４個以下の第一級および／または第二級アミノ基と水酸基を有する、数平均分子量５，０００以下のアミノアルコール類、
　（ｉｉｉ）２個以上４個以下の水酸基を有する、数平均分子量５，０００以下のポリエステルポリオール類、
　（ｉｖ）２個以上４個以下の水酸基を有する、数平均分子量５，０００以下の、ポリブタジエンポリオール類およびそれらと他のビニルモノマーとの共重合体、
　（ｖ）２個以上４個以下の水酸基を有する、数平均分子量５，０００以下の、ポリクロロプレンポリオール類およびそれらと他のビニルモノマーとの共重合体、
　（ｖｉ）２個以上４個以下の水酸基を有する、数平均分子量５，０００以下のポリエーテルポリオール類である、
　多価アミン、多価フェノールおよびアミノアルコール類のＣ２～Ｃ４のアルキレンオキサイド重付加物、Ｃ３以上の多価アルコール類のＣ２～Ｃ４のアルキレンオキサイド重付加物、Ｃ２～Ｃ４のアルキレンオキサイド共重合物、または、Ｃ３～Ｃ４のアルキレンオキサイド重合物。 2 or more and 4 of the residues from which the active hydrogen group of the polyol compound having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less, which is X in the general formula (1), is eliminated. 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.
(I) Multihydric alcohols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
(Ii) Amino alcohols having a number average molecular weight of 5,000 or less and having 2 or more and 4 or less primary and / or secondary amino groups and hydroxyl groups.
(Iii) Polyester polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
(Iv) Polybutadiene polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less, and copolymers thereof with other vinyl monomers.
(V) Polychloroprene polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less, and copolymers thereof with other vinyl monomers.
(Vi) Polyester polyols having 2 or more and 4 or less hydroxyl groups and having a number average molecular weight of 5,000 or less.
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.
　上記（Ｃ－２）成分は、特に限定されるものではないが、第一工業製薬（株）製のエラストロン　ＢＮ２７、ＢＮ７７、ＢＮ１１等の市販品を用いることもできる。中でも、エラストロンＢＮ７７が好ましい。 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.
＜（Ｄ）エポキシド化合物＞
　本発明の有機繊維用接着剤組成物の一実施態様は、（Ａ）不飽和ジエンを有するゴムラテックス、（Ｂ）カゼイン、および、（Ｄ）エポキシド化合物を含む。なお、この接着剤組成物は、レゾルシンを含まない。 <(D) Epoxide compound>
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.
　上記（Ｄ）エポキシド化合物とは、３員環のエーテルであるオキサシクロプロパン（オキシラン）（エポキシ基）を構造式中に持つ化合物を意味する。 The above (D) epoxide compound means a compound having oxacyclopropane (oxylan) (epoxy group), which is a 3-membered ring ether, in its structural formula.
　上記（Ｄ）エポキシド化合物は、上記有機繊維用接着剤組成物において、架橋剤成分として機能する。すなわち、接着剤組成物が（Ｄ）エポキシド化合物を含有すると、（Ｂ）カゼインのアミノ酸単位に含まれる水酸基、アミン基との間で、架橋が導入され、接着剤層の耐破壊抗力の向上および高温での接着力において著しい性能向上が見られるようになる。 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.
　また、上記（Ｄ）エポキシド化合物は、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物と混合して加熱することが好ましい。このような（Ｄ）エポキシド化合物と上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物とを混合して加熱すると、ウレタン結合を主とした上記有機繊維用接着剤組成物に、（Ｄ）エポキシド化合物のエポキシ基と、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物が有するアミン、アルコール、チオール、フェノール、カルボン酸、または、（熱解離性ブロックが解離した）イソシアネート等との求核反応による架橋が加わり、高温領域での応力によるクリープやフローが抑制されるようになるからである。 Further, it is preferable that the (D) epoxide compound is mixed with the above-mentioned (C) (thermally dissociative blocked) aqueous compound having an isocyanate group and heated. When such an (D) epoxide compound and the above (C) aqueous compound having an (heat-dissociable blocked) isocyanate group are mixed 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. This 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.
　さらにまた、上記（Ｄ）エポキシド化合物のエポキシ基は多官能であることが好ましい。上記抑制の効果が高まり、上記有機繊維用接着剤組成物による接着剤層の耐破壊抗力がより高まり、高温での接着力もより高くなるからである。 Furthermore, it is preferable that 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.
　上記（Ｄ）エポキシド化合物は、１分子中に２個以上のエポキシ基を含む化合物であることが好ましい。特に好ましくは１分子中に４個以上のエポキシ基を含む化合物である。この理由は、エポキシ基が多官能となることで、有機繊維用接着剤組成物において、高温領域での応力によるクリープやフローがより抑制され、接着剤層の耐破壊抗力がより高まって、高温での接着力もより高くなるからである。 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.
　上記（Ｄ）エポキシド化合物の具体例としては、例えば、ジエチレングリコール・ジグリシジルエーテル、ポリエチレングリコール・ジグリシジルエーテル、ポリプロピレングリコール・ジグリシジルエーテル、ネオペンチルグリコール・ジグリシジルエーテル、１，６－ヘキサンジオール・ジグリシジルエーテル、グリセロール・ポリグリシジルエーテル、トリメチロールプロパン・ポリグリシジルエーテル、ポリグリセロール・ポリグリシジルエーテル、ペンタエリチオール・ポリグリシジルエーテル、ジグリセロール・ポリグリシジルエーテル、ソルビトール・ポリグリシジルエーテル等の多価アルコール類と、エピクロロヒドリンとの反応生成物；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；ビスフェノールＡ型エポキシ樹脂等が挙げられる。好ましくは、多価アルコール類とエピクロロヒドリンとの反応生成物、または、ノボラック型エポキシ樹脂である。特に、上記（Ｄ）エポキシド化合物が、多価アルコール類とエピクロロヒドリンとの反応生成物であると、水に溶解または乳化により水に分散させて使用できることから、その製造がより容易であり、好ましい。上記ソルビトール・ポリグリシジルエーテル、ポリグリセロール・ポリグリシジルエーテル、ノボラック型エポキシ樹脂は、市販の薬品を用いることができる。 Specific examples of the (D) epoxide compound 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. And the reaction product with epichlorohydrin; novolak type epoxy resin such as phenol novolac type epoxy resin, cresol novolak type epoxy resin; bisphenol A type epoxy resin and the like. A reaction product of a polyhydric alcohol and epichlorohydrin, or a novolak type epoxy resin is preferable. In particular, when the epoxide compound (D) 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.
　上記（Ｄ）エポキシド化合物は、水に溶解させて、または、乳化により水に分散させて使用することができる。例えば、上記（Ｄ）エポキシド化合物をそのまま水に溶解することができる。または、上記（Ｄ）エポキシド化合物を必要に応じて少量の溶媒に溶解し、該溶解液を、公知の乳化剤、例えば、アルキルベンゼンスルホン酸ソーダ、ジオクチルスルホサクシネートナトリウム塩、ノニルフェノールエチレンオキサイド付加物等を用いて、水に乳化することで、乳化液とすることができる。 The above (D) epoxide compound can be used by dissolving it in water or dispersing it in water by emulsification. For example, the above (D) epoxide compound can be dissolved in water as it is. Alternatively, 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.
　本発明の有機繊維用接着剤組成物の固形分全体に占める、上記（Ｄ）エポキシド化合物の含有量（固形分含有率）は、特に限定されるものではないが、０．１質量％以上であることが好ましく、より好ましくは５質量％以上である。また、上記（Ｄ）エポキシド化合物の含有量（固形分含有率）は、４０質量％以下であることが好ましく、より好ましくは２５質量％以下である。含有量が０．１質量％以上であれば、樹脂と被覆ゴム組成物の接着性がより良好なものになるからである。また、含有量が４０質量％以下であれば、接着剤組成物に配合するゴムラテックス等の他の成分の量を、相対して一定以上確保することが可能となり、その結果、被着ゴムとの接着性がより良好となるからである。 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.
＜（Ｅ）ポリフェノール＞
　本発明の有機繊維用接着剤組成物の一実施態様は、（Ａ）不飽和ジエンを有するゴムラテックス、（Ｂ）カゼイン、および、（Ｅ）ポリフェノールを含む。なお、この接着剤組成物は、レゾルシンを含まない。また、この接着剤組成物は、ホルムアルデヒドを含まないことが好ましい。 <(E) Polyphenol>
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.
　上記（Ｅ）ポリフェノールとは、分子内に複数のフェノール性ヒドロキシ基を持つ植物由来の化合物であることが好ましい。この場合、有機繊維と被覆ゴム組成物の接着性がより良好となる。 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.
　木材や樹皮中の成分であるリグニンやタンニン等のポリフェノールを分離し、ホルムアルデヒドと反応させ接着剤を製造する研究（例えば、特開平０７－５３８５８号公報を参照）が古くから行われているが、レゾルシンを含まない水系接着剤組成物を製造する知見は少ない。 Research on separating polyphenols such as lignin and tannin, which are components in wood and bark, and reacting them with formaldehyde to produce an adhesive (see, for example, Japanese Patent Application Laid-Open No. 07-53858) has been conducted for a long time. There is little knowledge about producing water-based adhesive compositions that do not contain resorcin.
　上記（Ｅ）ポリフェノールは、リグニンあるいはその誘導体であることが好ましい。この場合も、有機繊維と被覆ゴム組成物の接着性がより良好となる。リグニンとは、セルロースなどの多糖類と共に、植物の植物体細胞壁を構成する主要成分である。リグニンは、例えば、ヒドロキシル基、メトキシ基、カルボニル基およびカルボキシル基などの官能基を含むが、特に、フェノール性のヒドロキシ基は反応性の高いものであることから、カゼインなどのカチオン性ポリマーと相互作用を持つことができる。 The above (E) polyphenol is preferably lignin or a derivative thereof. In this case as well, 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.
　リグニンは、フェニルプロパンに基づいた構造を有するポリマーであるが、リグニンの分子構造は様々であり、三次元網目構造を形成した、巨大な生体高分子であるので、その分子構造はいまだ完全には解明されていない。 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.
　天然のリグニンは、植物細胞壁中で、セルロースなどの多糖類と共に強固に複合材料を形成しているため、化学構造の変性を伴わない天然リグニンの単離は、非常に困難とされている。様々な工業的な分離方法が、木などの材料からリグニンを抽出するために使用されている。分離後に得られるリグニンは、スルホン酸リグニン、クラフトリグニン、ソーダリグニン、水蒸気爆砕リグニン等が挙げられる。これらの工業的に扱われているリグニンで、入手性・経済性の観点から、紙パルプ製造プロセスの化学パルプ化のパルプ廃液より大規模に得られるリグニン、すなわち、リグノスルホン酸塩、あるいはクラフトリグニンが周知の材料である。 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.
　それ以外のリグニン類の例としては、ヒドロキシメチル化、エポキシ化、脱窒素化、アシル化またはヒドロキシル化によって変性されたリグニン、ジエタノールアミン変性リグニン、酵素変性リグニン、ラッカーゼ変性リグニン、尿素変性リグニン、リグノスルホネート、アルセル法リグニン、アルカリグラニット法リグニン、ポリエチレングリコール付加リグニン、などが挙げられる。 Examples of other lignins 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.
　上記クラフトリグニンは、原料の木材としての、例えば、広葉樹、針葉樹、雑木、タケ、ケナフ、バガス等の木材チップを、水酸化ナトリウム／硫化ナトリウムなどによる蒸解液と共に蒸解釜へ投入することによる、高温高圧反応であるクラフト蒸解法と呼ばれる化学パルプ化法（高温高圧反応）由来のリグニンである。クラフト蒸解後に得られるクラフト廃液に酸および／または二酸化炭素を添加して、溶解しているリグニン変性物を沈殿させ、生成した沈殿物を脱水・洗浄して得られる。また、脱水・洗浄後の沈殿は、アルコールやアセトンなどの有機溶媒を添加して溶解させ、不溶物である不純物を分離させて乾燥する精製や、必要に応じて各種の官能基を導入させる変性を行うことができる。上記クラフトリグニンは、市販される製品を入手して使用することができる。 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. The above-mentioned craft lignin can be obtained and used as a commercially available product.
　上記スルホン酸リグニンは、木材チップを、亜硫酸および／または亜硫酸塩を用いた蒸解液とともに高温高圧反応させる亜硫蒸解法による化学パルプ化法において、亜硫酸パルプから溶出する廃液等を原料として得られるリグニンスルホン酸およびその塩であり、リグニンスルホン酸カルシウム、リグニンスルホン酸ナトリウム、リグニンスルホン酸カリウム、リグニンスルホン酸マグネシウム塩が特に好ましく挙げられる。中でも、リグニンスルホン酸ナトリウム等が好ましい。これらスルホン酸リグニンは市販品として入手でき、例えば、リグニンスルホン酸塩あるいは変性リグニンスルホン酸塩としては、日本製紙株式会社製品のサンエキスシリーズなどを用いることができる。 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.
　リグニンスルホン酸塩の高付加価値品としては、例えば、高純度品はもちろんのこと、リグニンスルホン酸塩を水酸化ナトリウムまたはアンモニアを使用するアルカリ性水溶液中で、酸素等の酸化剤の存在下で加熱する方法（例えば、特開２０１６－１３５８３４号公報などを参照）により、スルホン化度を低減させた部分脱（低）スルホン化リグニンスルホン酸塩が挙げられる。高純度のリグニンスルホン酸塩あるいは変性リグニンスルホン酸塩としては、日本製紙株式会社製品のパールレックスシリーズ、部分脱スルホンリグニンスルホン酸としては、日本製紙株式会社製品のバニレックスシリーズなどを用いることができる。中でも、スルホン化度を低減させた部分脱（低）スルホン化リグニンスルホン酸塩である、東京化成工業株式会社製、試薬名「リグニン（アルカリ）」（ＣＡＳ　Ｎｕｍｂｅｒ：８０６１－５１－６、固形粉体）が好ましい。 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. (For example, see Japanese Patent Application Laid-Open No. 2016-135834), examples thereof include partially de-(low) sulfonated lignin sulfonate having a reduced degree of sulfonate. As the high-purity lignin sulfonate or modified lignin sulfonate, the Pearllex series manufactured by Nippon Paper Industries, Ltd. can be used, and as the partially desulfoned lignin sulfonate, 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.
　本発明の有機繊維用接着剤組成物の固形分全体に占める、上記（Ｅ）ポリフェノールの含有量（固形分含有率）は、特に限定はされるものではないが、２質量％以上であることが好ましく、５質量％以上であることがより好ましく、７質量％以上であることがさらに好ましい。また、上記（Ｅ）ポリフェノールの含有量は、７５質量％以下であることが好ましく、５０質量％以下であることがより好ましく、３５質量％以下であることがさらに好ましい。上記（Ｅ）ポリフェノールの含有量が、２質量％以上であれば、有機繊維と被覆ゴム組成物の接着性がより良好なものになるからである。また、上記（Ｅ）ポリフェノールの含有量が、７５質量％以下であれば、有機繊維用接着剤組成物に配合するゴムラテックス等の他の成分の量を、相対して一定以上確保することが可能となり、その結果、被着ゴムとの接着性がより良好となるからである。 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. Further, when the content of the (E) polyphenol is 75% by mass or less, 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.
＜有機繊維用接着剤組成物の製造方法＞
　本発明の有機繊維用接着剤組成物は、（Ａ）不飽和ジエンを有するゴムラテックス、（Ｂ）カゼイン、並びに、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物および（Ｅ）ポリフェノールからなる群から選ばれる化合物を１つ以上含むことを特徴とする。上記有機繊維用接着剤組成物を製造するにあたっては、これら（Ａ）不飽和ジエンを有するゴムラテックス、（Ｂ）カゼイン、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物、および、（Ｅ）ポリフェノールを、任意の順序で混合することができる。 <Manufacturing method of adhesive composition for organic fibers>
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. In producing the adhesive composition for organic fibers, these (A) rubber latex having an unsaturated diene, (B) casein, (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group, and (D) ) The epoxide compound and (E) the polyphenol can be mixed in any order.
　但し、上記（Ｄ）エポキシド化合物は、水と混合すると、エポキシ基が水と反応して、次第に架橋剤としての機能が失活していく傾向がある。そのため、上記（Ｄ）エポキシド化合物を水と混合した後には、当該有機繊維用接着剤組成物を、なるべく早く、有機繊維の被覆処理に供することが好ましい。具体的には、上記（Ｄ）エポキシド化合物を水と混合した後、２日以内に、当該有機繊維用接着剤組成物を、有機繊維の被覆処理に供することが好ましく、１日以内がより好ましい。 However, when the above (D) epoxide compound is mixed with water, the epoxy group reacts with water, and the function as a cross-linking agent tends to be gradually deactivated. Therefore, after mixing the epoxide compound (D) with water, it is preferable that 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. ..
　本発明の有機繊維用接着剤組成物において、（Ａ）不飽和ジエンを有するゴムラテックスと（Ｂ）カゼインとの混合質量比［（Ａ）：（Ｂ）］（固形分換算）は、特に限定されるものではないが、１００：０．１から１００：２５の範囲にあることが好ましく、１００：０．２から１００：５の範囲にあることがより好ましい。 In the adhesive composition for organic fibers of the present invention, 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.
　上記混合質量比が、１００：０．１以上であれば（比の値として１０００以下であれば）、（Ａ）不飽和ジエンを有するゴムラテックスをコアとして、その周囲に（Ｂ）カゼインのマイクロカプセルの皮膜を形成することができ、かつ、十分な強度の接着剤層を得ることもできるからである。また、上記混合質量比が、１００：２５以下であれば（比の値として４以上であれば）、（Ａ）不飽和ジエンを有するゴムラテックスをコアとして、その周囲に形成される（Ｂ）カゼインのマイクロカプセルの皮膜が厚くなりすぎず、有機繊維の被着体である被覆ゴム組成物と有機繊維用接着剤組成物とを共加硫して接着させる際に、上記被着体である被覆ゴム組成物と上記（Ａ）不飽和ジエンを有するゴムラテックスとが良好に相溶し、その結果、上記被着体である被覆ゴム組成物と上記有機繊維用接着剤組成物との間の接着の初期過程が好適に進行するからである。 If 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.
　上記（Ａ）不飽和ジエンを有するゴムラテックスと上記（Ｂ）カゼインとの混合においては、通常のコアセルベートで、（Ｂ）カゼインからなる皮膜を強化できる公知の水溶性材料を併用することができる。例えば、アラビアガム、カラギーナン、ＣＭＣ類、有機または無機の塩からなる電解質物質、例えば、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化アンモニウムのような陽イオンを有する塩、硫酸塩、リン酸塩、炭酸塩、酢酸塩のような陰イオンを有する塩を使用することができる。さらに、水溶解性の液体であって、その中の皮膜形成材料が水よりも少なく溶解するような液体物質、例えば、エタノール、プロパノールのようなアルコール類、または、イソブチレン－無水マレイン酸開環共重合体塩などの水溶性高分子類を使用することもできる。 In the mixing of the rubber latex having (A) unsaturated diene and the above (B) casein, a known water-soluble material capable of strengthening the film composed of (B) casein can be used in combination with ordinary coacervates. For example, 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. Furthermore, 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.
　本発明の有機繊維用接着剤組成物において、（Ａ）不飽和ジエンを有するゴムラテックスと、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物および（Ｅ）ポリフェノールからなる群から選ばれる化合物との混合質量比［（Ａ）：〔（Ｃ）＋（Ｄ）＋（Ｅ）〕］（固形分換算）は、特に限定されるものではないが、１００：５から１００：３００の範囲にあることが好ましく、１００：１０から１００：１５０の範囲にあることがより好ましく、１００：１５から１００：６０の範囲にあることがさらにより好ましい。 In the adhesive composition for organic fibers of the present invention, (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). 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.
　上記混合質量比が、１００：５以上であれば（比の値として２０以下であれば）、有機繊維用接着剤組成物中における（Ａ）不飽和ジエンを有するゴムラテックスが占める比が大きくなりすぎず、上記有機繊維用接着剤組成物による接着剤層の耐破壊抗力を十分に保つことができ、歪下での接着性の低下を防止することができるからである。また、上記混合質量比が、１００：３００以下であれば（比の値として１／３以上であれば）、有機繊維用接着剤組成物中における（Ａ）不飽和ジエンを有するゴムラテックスが占める比が低くなりすぎず、有機繊維の被着体である被覆ゴム組成物と有機繊維用接着剤組成物とを共加硫して接着させる際に、上記被着体である被覆ゴム組成物と上記（Ａ）不飽和ジエンを有するゴムラテックスとが良好に相溶し、その結果、上記被着体である被覆ゴム組成物と上記有機繊維用接着剤組成物との間の接着性が十分に高いものとなるからである。 When the mixed mass ratio is 100: 5 or more (when the ratio value is 20 or less), 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. When the coated rubber composition, which is an adherend of organic fibers, and 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.
　また、上記（Ａ）不飽和ジエンを有するゴムラテックス、（Ｂ）カゼイン、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物、および、（Ｅ）ポリフェノールは、水性であることが好ましい。環境への汚染が少ない水を溶媒に使用することができるからである。 Further, 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.
［有機繊維－ゴム複合体］
　本発明の有機繊維－ゴム複合体は、有機繊維とゴムとの複合体であって、該有機繊維が、上記有機繊維用接着剤組成物により被覆されていることを特徴とするものである。これにより、レゾルシンを用いることなく良好な接着性を得ることができ、環境性や作業性が良好な有機繊維－ゴム複合体とすることができる。 [Organic fiber-rubber complex]
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.
　本発明の有機繊維－ゴム複合体を、図４を参照しながら、詳細に説明する。 The organic fiber-rubber complex of the present invention will be described in detail with reference to FIG.
　図４は、本発明の有機繊維－ゴム複合体の一例の有機繊維コード－ゴム複合体を示す断面概略図である。図４に示す有機繊維－ゴム複合体３１は、有機繊維コード１の外径方向外側表面が、本発明の有機繊維用接着剤組成物２による接着剤層３２で被覆されている。そして、上記有機繊維コード１は、上記有機繊維用接着剤組成物２による接着剤層３２を介して、さらにその外径方向外側にある被覆ゴム組成物３３と接着し、本発明の有機繊維－ゴム複合体３１が形成される。 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. In the organic fiber-rubber composite 31 shown in FIG. 4, 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.
　なお、本発明の有機繊維用接着剤組成物を用いたゴム物品の補強材の形態としては、上記有機繊維－ゴム複合体に加えて、フィルム、短繊維、不織布等の形態とすることもできる。 In addition to the above-mentioned organic fiber-rubber composite, 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. ..
＜＜有機繊維－ゴム複合体の有機繊維コード＞＞
　本発明の有機繊維－ゴム複合体を構成する有機繊維コードについては、前述したとおりとすることができる。 << 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.
＜＜有機繊維－ゴム複合体の被覆ゴム組成物＞＞
　本発明の有機繊維－ゴム複合体を構成する被覆ゴム組成物は、ゴム成分に、通常ゴム業界で用いられる各種配合剤を配合したものが好ましい。ここで、ゴム成分としては、特に限定はなく、例えば、天然ゴムの他、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレン－ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル－ブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）等の共役ジエン系合成ゴム、さらには、エチレン－プロピレン共重合体ゴム（ＥＰＭ）、エチレン－プロピレン－ジエン共重合体ゴム（ＥＰＤＭ）、ポリシロキサンゴム等が挙げられる。これらの中でも、天然ゴムおよび共役ジエン系合成ゴムが好ましい。また、これらゴム成分は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 << Organic fiber-rubber composite coated rubber composition >>
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. Here, the rubber component is not particularly limited, and for example, in addition to natural rubber, polyisoprene rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), and acrylonitrile-butadiene rubber (NBR). ), Chloroprene rubber (CR), butyl rubber (IIR) and other conjugated diene synthetic rubber, as well as ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), polysiloxane rubber. And so on. Among these, natural rubber and conjugated diene-based synthetic rubber are preferable. Further, these rubber components may be used alone or in combination of two or more.
＜＜有機繊維－ゴム複合体の製造方法＞＞
　本発明の有機繊維－ゴム複合体は、有機繊維コード等の有機繊維を、本発明の有機繊維用接着剤組成物により被覆して接着剤層を形成し、上記有機繊維用接着剤組成物中の（Ａ）不飽和ジエンを有するゴムラテックスと、上記有機繊維の被着体である被覆ゴム組成物中のゴム成分とを共加硫して接着させることにより、製造することができる。 << Manufacturing method of organic fiber-rubber complex >>
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. (A) It can be produced by co-vulcanizing and adhering a rubber latex having an unsaturated diene and a rubber component in a coated rubber composition which is an adherend of the organic fiber.
　上記有機繊維を、本発明の有機繊維用接着剤組成物で被覆する方法としては、特に限定されるものではないが、上記有機繊維用接着剤組成物に上記有機繊維を浸漬する方法、上記有機繊維用接着剤組成物を上記有機繊維にハケなどにより塗布する方法、上記有機繊維用接着剤組成物を上記有機繊維にスプレーする方法等が挙げられ、必要に応じて適切な方法を選択することができる。 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.
　上記有機繊維を上記有機繊維用接着剤組成物により被覆する際には、上記有機繊維用接着剤組成物を種々の溶剤に溶解して粘度を下げると、被覆が容易になるため好ましい。上記有機繊維用接着剤組成物の粘度を下げるための溶剤は、主に水からなると、環境的に好ましい。 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.
　ここで、上記有機繊維用接着剤組成物による接着剤層の厚さは、特に限定されるものではないが、５０μｍ以下であることが好ましく、０．５μｍ以上、３０μｍ以下であることがより好ましい。 Here, the thickness of the adhesive layer by the adhesive composition for organic fibers is not particularly limited, but is preferably 50 μm or less, more preferably 0.5 μm or more and 30 μm or less. ..
　なお、接着処理による接着剤組成物の付着量が厚くなると、タイヤ転動下での接着耐久性が低下する傾向がある。この理由は、被着する繊維材料の界面の接着剤組成物は、繊維材料の剛性が高いため歪による応力を負担することにより比較的変形が小さくなるが、界面から離れるに従って歪による変形が大きくなるためである。被着ゴム材料に比べて接着剤組成物は熱硬化性縮合物を多く含むため、硬く脆いことにより繰り返し歪下での接着疲労が大きくなりやすい。以上より、接着剤組成物層の平均厚さは、５０μｍ以下であることが好ましく、０．５μｍ以上、３０μｍ以下であることがより好ましい。 If the amount of the adhesive composition adhered by the adhesive treatment becomes large, the adhesive durability under tire rolling tends to decrease. The reason for this is that the adhesive composition at the interface of the fiber material to be adhered has relatively small deformation due to the stress due to strain due to the high rigidity of the fiber material, but the deformation due to strain increases as the distance from the interface increases. This is to become. 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 μm or less, and more preferably 0.5 μm or more and 30 μm or less.
　また、上記有機繊維に含浸した有機繊維用接着剤組成物の濃度は、特に限定されるものではないが、上記有機繊維の質量に対して、固形分換算値で、５．０質量％以上、２５．０質量％以下であることが好ましく、７．５質量％以上、２０．０質量％以下であることがより好ましい。 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.
　上記有機繊維用接着剤組成物で被覆した有機繊維は、例えば、１００℃以上、２１０℃以下の温度で乾燥させた後、有機繊維の高分子鎖のガラス転移温度（典型的には、該高分子鎖の〔融解温度：－７０℃〕）以上、〔融解温度：－１０℃〕以下の温度）以上で熱処理を行うことが好ましい。この好ましい理由としては、上記有機繊維の高分子鎖のガラス転移温度以上であれば、上記有機繊維の高分子鎖の分子運動性が良好となり、上記有機繊維用接着剤組成物の中の接着促進剤（例えば、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物）と、上記有機繊維の高分子鎖とが、十分な相互作用を行えるために、上記有機繊維用接着剤組成物と上記有機繊維との間の接着力が十分に得られるからである。上記有機繊維は、あらかじめ電子線、マイクロ波、コロナ放電、プラズマ処理等により前処理加工されたものでもよい。 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.
　本発明の有機繊維－ゴム複合体において、樹脂材料は、コード、ケーブル、フィラメント、フィラメントチップ、コード織物、帆布等のいずれの形態でもよい。特に、タイヤ物品やコンベヤベルト等のゴム物品の補強には、上記樹脂材料として、複数のフィラメントを撚り合わせてなるコードが好適に用いられる。 In the organic fiber-rubber composite of the present invention, 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. In particular, for reinforcing rubber articles such as tire articles and conveyor belts, a cord made by twisting a plurality of filaments is preferably used as the resin material.
　本発明においては、上記有機繊維が、撚構造１４００ｄｔｅｘ／２、上撚数３９回／１０ｃｍ、下撚数３９回／１０ｃｍの６６ナイロンのタイヤコードであり、このタイヤコードに上記有機繊維用接着剤組成物を付着させた、有機繊維－ゴム複合体であることが好ましい。 In the present invention, 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.
　最後に、上記有機繊維用接着剤組成物で被覆した有機繊維は、上記有機繊維用接着剤組成物中の（Ａ）不飽和ジエンを有するゴムラテックスと、上記有機繊維の被着体である被覆ゴム組成物中のゴム成分とを共加硫して接着させる。 Finally, 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.
　上記被覆ゴム組成物中のゴム成分の共加硫には、例えば、硫黄、テトラメチルチラリウムジスルフィド、ジペンタメチレンチラリウムテトラサルファイド等のチラリウムポリサルファイド化合物、４，４－ジチオモルフォリン、ｐ－キノンジオキシム、ｐ，ｐ’－ジベンゾキノンジオキシム、環式硫黄イミドなど有機加硫剤を用いることができる。中でも、硫黄を用いることが好ましい。また、上記被覆ゴム組成物中のゴム成分には、ゴム業界で通常用いられるカーボンブラック、シリカ、水酸化アルミニウム等の充填剤、加硫促進剤、老化防止剤、軟化剤等の各種配合剤を、適宜配合することができる。 For co-vulcanization of the rubber component in the coated rubber composition, 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 can be used. Above all, it is preferable to use sulfur. Further, as the rubber component in the coated rubber composition, 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.
　また、本発明の有機繊維用接着剤組成物は、有機繊維等の合成樹脂材料の被着体および／または被覆ゴム組成物の被着体に含まれる加硫剤が上記有機繊維用接着剤組成物へ移行し、移行してきた上記加硫剤により上記有機繊維用接着剤組成物が架橋される接着方法においても、接着の効果が得られることは言うまでもない。 Further, in the adhesive composition for organic fibers of the present invention, 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. Needless to say, 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.
［タイヤ］
　本発明のタイヤは、本発明の有機繊維－ゴム複合体を用いたものである。これにより、レゾルシンを用いることなく良好な接着性を得ることができ、環境性や作業性が良好なタイヤとすることができる。 [tire]
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.
　ここで、本発明のタイヤにおいて、上記有機繊維－ゴム複合体は、例えば、カーカス、ベルト、ベルト補強層、フリッパー等のベルト周りの補強層として用いることが可能である。 Here, in the tire of the present invention, 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.
　本発明のタイヤは、適用するタイヤの種類に応じ、未加硫のゴム組成物を用いて成形後に加硫して得てもよく、または、予備加硫工程等を経た半加硫ゴムを用いて成形後、さらに本加硫して得てもよい。なお、本発明のタイヤには、当該タイヤのいずれかの箇所に、上述の接着剤組成物で処理した有機繊維が用いられるが、その他の部材は、特に限定されず、公知の部材を使用することができる。また、本発明のタイヤは、空気入りタイヤであることが好ましく、この空気入りタイヤに充填する気体としては、通常の、または、酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウム等の不活性ガスを用いることができる。 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. In the tire of the present invention, 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. Further, 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.
　なお、上述した、本発明の有機繊維用接着剤組成物、および、本発明の有機繊維－ゴム複合体は、上記タイヤに加えて、コンベヤベルト、ベルト、ホース、空気バネ等のあらゆるゴム物品にも適用することができる。 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.
　以下に、実施例を挙げて本発明をさらに詳しく説明するが、本発明は下記の実施例により、何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
＜（Ａ）不飽和ジエンを有するゴムラテックス＞
　以下の比較例および実施例においては、（Ａ）不飽和ジエンを有するゴムラテックスとして、ビニルピリジン－スチレン－ブタジエン共重合体ラテックスを、特開平９－７８０４５号公報に記載の比較例１に準拠して、以下の通り調製し、使用した。 <(A) Rubber latex with unsaturated diene>
In the following Comparative Examples and Examples, (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.
　窒素置換した５リットル容量のオートクレーブに、脱イオン水１３０質量部、乳化剤としてのロジン酸カリウム４．０質量部を仕込み溶解した。これに、ビニルピリジン単量体１５質量部、スチレン１５質量部およびブタジエン７０質量部組成の単量体混合物と、連鎖移動剤としてのｔ－ドデシルメルカプタン０．６０質量部を仕込み、乳化した。その後、５０℃に昇温させ、重合開始剤としての過硫酸カリウム０．５質量部を加え、重合を開始した。単量体混合物の反応率が９０％に達した後、ハイドロキノン０．１質量部を加え、重合を停止した。次に、減圧下、未反応単量体を除去し、固形分濃度４１質量％のビニルピリジン－スチレン－ブタジエン共重合体ラテックスを得た。 130 parts by mass of deionized water and 4.0 parts by mass of potassium rosinate as an emulsifier were charged and dissolved in a 5 liter volume autoclave substituted with nitrogen. To this, a monomer mixture having a composition of 15 parts by mass of vinylpyridine monomer, 15 parts by mass of styrene and 70 parts by mass of butadiene, and 0.60 parts by mass of t-dodecyl mercaptan as a chain transfer agent were charged and emulsified. Then, the temperature was raised to 50 ° C., 0.5 part by mass of potassium persulfate as a polymerization initiator was added, and polymerization was started. After the reaction rate of the monomer mixture reached 90%, 0.1 part by mass of hydroquinone was added to terminate the polymerization. Next, the unreacted monomer was removed under reduced pressure to obtain a vinylpyridine-styrene-butadiene copolymer latex having a solid content concentration of 41% by mass.
＜（Ｂ）カゼイン＞
　以下の実施例においては、（Ｂ）カゼインとして、等電沈殿カゼイン（酸カゼイン）である、ナカライテスク株式会社製の試薬名「カゼイン（牛乳製）」（粉末固体）の５ｇを、脱イオン水７０ｇの水中で懸濁させながら、中和溶解用のアルカリとして関東化学株式会社製の試薬名「１ｍｏｌ／Ｌアンモニア水」（容量分析用滴定用規定濃度溶液）を２５ｇ添加して、液温５５℃にて透明となるまで溶解させ、カゼイン固形分濃度が５質量％の水溶液を製造し、この水溶液を接着剤組成物の調製に使用した。 <(B) Casein>
In the following examples, as (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.
＜（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物＞
　以下の比較例２および実施例１，５においては、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物として、第一工業製薬株式会社製の商品名「エラストロンＢＮ７７（Ｆ－２９５５Ｄ－１）」（（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物、ブロック剤熱解離温度：約１６０℃、ｐＨ：８．０、固形分濃度：３１質量％）をそのまま用いた。 <(C) (Thermal dissociative blocked) Aqueous compound having an isocyanate group>
In Comparative Examples 2 and 1 and 5 below, as the aqueous compound having (C) (heat dissociable blocked) isocyanate group, the trade name "Elastron BN77 (F-2955D-)" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 1) ”((C-2) (heat dissociable blocked) aqueous urethane compound having an isocyanate group, blocking agent heat dissociation temperature: about 160 ° C., pH: 8.0, solid content concentration: 31% by mass) as it is Using.
＜（Ｄ）エポキシド化合物＞
　以下の比較例３および実施例２，６においては、（Ｄ）エポキシド化合物として、ソルビトール・ポリグリシジルエーテルである、ナガセケムテックス（株）製の商品名「デナコールＥＸ－６１４Ｂ」（分子量：９４９、エポキシ当量：１７３、固形分濃度：１００質量％）を、脱イオン水で希釈して、固形分濃度１０質量％の水溶液としたものを、接着剤組成物の調製に使用した。 <(D) Epoxide compound>
In Comparative Example 3 and Examples 2 and 6 below, the trade name "Denacol EX-614B" (molecular weight: 949,) manufactured by Nagase ChemteX Corporation, which is a sorbitol polyglycidyl ether as the (D) epoxide compound, is used. Epoxy equivalent: 173, solid content concentration: 100% by mass) was diluted with deionized water to obtain an aqueous solution having a solid content concentration of 10% by mass, which was used for preparing the adhesive composition.
＜（Ｅ）ポリフェノール＞
　以下の比較例４，５および実施例３～６においては、（Ｅ）ポリフェノールとして、東京化成工業株式会社製の商品名「リグニン（アルカリ）」（ＣＡＳ　Ｎｕｍｂｅｒ：８０６１－５１－６）（スルホン化度を低減させた部分脱スルホン化リグニンスルホン酸塩）、および、Ｓｉｇｍａ－Ａｌｄｒｉｃｈ　Ｃｏ．ＬＬＣ社製の製品名「Ｌｉｇｎｉｎ，ａｌｋａｌｉ」（ＣＡＳ　Ｎｕｍｂｅｒ　８０６８－０５－１、固形粉体）（クラフトリグニン）を、脱イオン水で希釈して、固形分濃度１０質量％の水溶液としたものを、接着剤組成物の調製に使用した。 <(E) Polyphenol>
In the following Comparative Examples 4 and 5 and Examples 3 to 6, the trade name "lignin (alkali)" (CAS Number: 8061-51-6) (sulfonated) manufactured by Tokyo Kasei Kogyo Co., Ltd. as (E) polyphenol. Partially desulfonated lignin sulfonate), and Sigma-Aldrich Co., Ltd. The product name "Ligin, alkali" (CAS Number 8068-05-1, solid powder) (craft lignin) manufactured by LLC was diluted with deionized water to obtain an aqueous solution having a solid content concentration of 10% by mass. , Used to prepare the adhesive composition.
＜＜ラテックス接着剤組成物（比較例１）の調製＞＞
　上記（Ａ）不飽和ジエンを有するゴムラテックスと、水とを、固形分濃度が１８質量％となるように量を調節して混合した後、十分に攪拌を行い、ラテックス接着剤組成物（比較例１）を得た。 << Preparation of Latex Adhesive Composition (Comparative Example 1) >>
The rubber latex having (A) unsaturated diene and water were mixed by adjusting the amount so that the solid content concentration was 18% by mass, and then sufficiently stirred to make a latex adhesive composition (comparative). Example 1) was obtained.
＜＜ラテックス－水性ウレタン接着剤組成物（比較例２）の調製＞＞
　上記（Ａ）不飽和ジエンを有するゴムラテックスと、上記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物とを、表２に示すように配合し、接着剤組成物の固形分濃度が１８質量％となるように水で量を調節して混合した後、十分に攪拌を行い、ラテックス－水性ウレタン接着剤組成物（比較例２）を得た。 << Preparation of 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).
＜＜ラテックス－エポキシド接着剤組成物（比較例３）の調製＞＞
　上記（Ａ）不飽和ジエンを有するゴムラテックスと、上記（Ｄ）エポキシド化合物とを、表２に示すように配合し、接着剤組成物の固形分濃度が１８質量％となるように水で量を調節して混合した後、十分に攪拌を行い、ラテックス－エポキシド接着剤組成物（比較例３）を得た。 << Preparation of 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).
＜＜ラテックス－ポリフェノール接着剤組成物（比較例４，５）の調製＞＞
　上記（Ａ）不飽和ジエンを有するゴムラテックスと、上記（Ｅ）ポリフェノールとを、表２に示すように配合し、接着剤組成物の固形分濃度が１８質量％となるように水で量を調節して混合した後、十分に攪拌を行い、ラテックス－ポリフェノール接着剤組成物（比較例４，５）を得た。 << Preparation of 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).
＜＜本発明の一実施形態である有機繊維用接着剤組成物（実施例１～６）の調製＞＞
　表３に示すように、各所定の（Ａ）不飽和ジエンを有するゴムラテックスおよび（Ｂ）カゼインと、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物（実施例１，５）、（Ｄ）エポキシド化合物（実施例２，６）および（Ｅ）ポリフェノール（実施例３～６）とを、この順番にて配合し、接着剤組成物の固形分濃度が１８質量％となるように水で量を調節して混合した後、十分に攪拌を行い、本発明の一実施形態である有機繊維用接着剤組成物（実施例１～６）を得た。 << Preparation of Adhesive Compositions for Organic Fibers (Examples 1 to 6), which is an embodiment of the present invention >>
As shown in Table 3, each predetermined (A) rubber latex having an unsaturated diene and (B) casein, and (C) an aqueous compound having a (thermally dissociable blocked) isocyanate group (Examples 1 and 5). , (D) epoxide compounds (Examples 2 and 6) and (E) polyphenols (Examples 3 to 6) are blended in this order so that the solid content concentration of the adhesive composition is 18% by mass. After adjusting the amount with water and mixing, the mixture was sufficiently stirred to obtain an adhesive composition for organic fibers (Examples 1 to 6) according to an embodiment of the present invention.
＜タイヤコードの、各有機繊維用接着剤組成物による被覆＞
　有機繊維として、撚構造１６７０ｄｔｅｘ／２、上撚数３９回／１０ｃｍ、下撚数３９回／１０ｃｍのポリエチレンテレフタレート製のタイヤコードを用いた。 <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.
　上記タイヤコードを、比較例１～５および実施例１～６の各有機繊維用接着剤組成物に浸漬し、タイヤコードに含浸した有機繊維用接着剤組成物の濃度が、上記有機繊維の質量に対して３．８質量％となるようにした。次いで、乾燥ゾーンにおける乾燥（１５０℃、６０秒）、ホットゾーンにおける張力（０．８ｋｇ／本）を加えながらの樹脂の熱硬化、ノルマライズゾーンにおける上記張力を緩めながらの熱硬化（２４０℃、６０秒）に順次供して、比較例１～５および実施例１～６の各有機繊維用接着剤組成物で被覆されたタイヤコードを取得した。 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.
＜タイヤコード－ゴム複合体の作製＞
　上記比較例１～５および実施例１～６の各有機繊維用接着剤組成物で被覆されたタイヤコードを、未加硫のゴム組成物に埋め込み、１５５℃×２０分で共加硫した。なお、被覆用の未加硫のゴム組成物としては、天然ゴム、スチレン－ブタジエンゴム、カーボンブラックおよび加硫系薬品等を含むゴム組成物を用いた。 <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. As the unvulcanized rubber composition for coating, a rubber composition containing natural rubber, styrene-butadiene rubber, carbon black, vulcanized chemicals and the like was used.
＜有機繊維用接着剤組成物の作業性評価＞
　比較例１～５および実施例１～６の各有機繊維用接着剤組成物の作業性に関して、以下の評価を行った。 <Evaluation of workability of adhesive composition for organic fibers>
The workability of each of the adhesive compositions for organic fibers of Comparative Examples 1 to 5 and Examples 1 to 6 was evaluated as follows.
＜＜機械的安定性（凝固率）の評価＞＞
　各有機繊維用接着剤組成物の機械的安定性（凝固率）を、ＪＩＳ　Ｋ６３９２－１９９５に示される共重合体ラテックス組成物のマロン式機械的安定度試験機（熊谷理機工業株式会社製、マーロン安定度試験機Ｎｏ．２３１２－ＩＩ）を用いた方法に準拠して、測定した。 << Evaluation of mechanical stability (coagulation rate) >>
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).
　概述すると、各有機繊維用接着剤組成物に、上記マロン式機械的安定度試験機のローターを用いて、圧縮荷重１０ｋｇ、回転数１０００ｒ／ｍｉｎで１０分間のせん断歪を与えた後、発生した凝固物量から、以下の式にて凝固率（％）を評価した。数値が小さい方が、機械的安定性に優れることを示す。
　凝固率（％）＝［（発生した凝固物の乾燥質量）／（供試の接着剤液の固形分質量）］×１００ Generally speaking, it was generated after applying shear strain to each organic fiber adhesive composition for 10 minutes at a compressive load of 10 kg and a rotation speed of 1000 r / min using the rotor of the Maron type mechanical stability tester. From the amount of solidified material, the coagulation rate (%) was evaluated by the following formula. The smaller the value, the better the mechanical stability.
Coagulation rate (%) = [(dry mass of generated coagulated product) / (solid content mass of adhesive liquid under test)] x 100
＜＜絞りロールへの付着性の評価＞＞
　有機繊維である上記ポリエチレンテレフタレートタイヤコードについて、各有機繊維用接着剤組成物を貯留する浸漬処理機にて、２０００ｍ連続処理をし、上記絞りロール上に各有機繊維用接着剤組成物が付着した量を目視し、次の５段階で評価した。
　　特大：特に多い。
　　大：多い。
　　中：中程度。
　　少：少ない。
　　微少：非常に少ない。 << Evaluation of Adhesion to Squeeze Roll >>
The polyethylene terephthalate tire cord, which is an organic fiber, was continuously treated for 2000 m with a dipping treatment machine for storing the adhesive composition for each organic fiber, and the adhesive composition for each organic fiber adhered to the drawing roll. The amount was visually inspected and evaluated in the following five stages.
Oversized: Especially many.
Large: Many.
Medium: Medium.
Low: Low.
Fine: Very few.
＜有機繊維用接着剤組成物の接着性評価＞
　各有機繊維用接着剤組成物の接着性に関して、以下の評価を行った。 <Evaluation of adhesiveness of adhesive composition for organic fibers>
The following evaluations were made regarding the adhesiveness of each organic fiber adhesive composition.
＜＜接着力の評価＞＞
　各有機繊維用接着剤組成物を使用して得られたタイヤコード－ゴム複合体を３００ｍｍ／分の速度にて引張することで、タイヤコードを上記タイヤコード－ゴム複合体から剥離し、タイヤコード１本あたりの剥離抗力を求めて、これを接着力（Ｎ／本）とした。 << Evaluation of adhesive strength >>
By pulling the tire cord-rubber composite obtained by using each organic fiber adhesive composition at a speed of 300 mm / min, the tire cord is peeled off from the tire cord-rubber composite, and the tire cord is removed. The peeling drag per piece was obtained and used as the adhesive force (N / piece).
＜＜被覆ゴムの付着状態の評価＞＞
　上記タイヤコード－ゴム複合体から剥離させたタイヤコードについて、被覆ゴムの付着状態を目視観察し、下記表１に従いスコア付けを行った。 << Evaluation of the adhesion state of the coated rubber >>
With respect to the tire cord peeled from the tire cord-rubber composite, the adhered state of the coated rubber was visually observed and scored according to Table 1 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
＜有機繊維用接着剤組成物の作業性評価および接着性評価の結果＞
　各比較例および実施例の有機繊維用接着剤組成物の各配合と、その作業性評価および接着性評価の結果とを、下記表２，３に示す。 <Results of workability evaluation and adhesiveness evaluation of adhesive composition for organic fibers>
The formulations of the organic fiber adhesive compositions of Comparative Examples and Examples, and the results of the workability evaluation and the adhesiveness evaluation are shown in Tables 2 and 3 below.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
＊Ａ１）ビニルピリジンラテックス：上記の方法で合成したビニルピリジン－スチレン－ブタジエン共重合体ラテックス（固形分濃度４１質量％）
＊Ｂ１）酸カゼイン：ナカライテスク株式会社製、試薬名「カゼイン（牛乳製）」（粉末固体）等電沈殿カゼイン（酸カゼイン）
＊Ｃ１）水性ウレタン化合物：第一工業製薬株式会社製、商品名「エラストロンＢＮ７７（Ｆ－２９５５Ｄ－１）」（ブロック剤熱解離温度：約１６０℃、ｐＨ８．０、固形分濃度３１質量％）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物
＊Ｄ１）エポキシド化合物：ナガセケムテックス（株）製、商品名「デナコールＥＸ－６１４Ｂ」（分子量９４９、エポキシ当量１７３、固形分濃度１０質量％）ソルビトール・ポリグリシジルエーテル
＊Ｅ１）ポリフェノール：東京化成工業株式会社製、商品名「リグニン（アルカリ）」（ＣＡＳ　Ｎｕｍｂｅｒ：８０６１－５１－６）スルホン化度を低減させた部分脱スルホン化リグニンスルホン酸塩
＊Ｅ２）ポリフェノール：Ｓｉｇｍａ－Ａｌｄｒｉｃｈ　Ｃｏ．ＬＬＣ社製の、製品名「Ｌｉｇｎｉｎ，ａｌｋａｌｉ」（ＣＡＳ　Ｎｕｍｂｅｒ　８０６８－０５－１）クラフトリグニン * A1) 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.
* C1) 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) Aqueous urethane compound having an isocyanate group * D1) 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-Aldrich Co., Ltd. Product name "Lignin, alkali" (CAS Number 8068-05-1) craft lignin manufactured by LLC.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表２，３から、（Ａ）不飽和ジエンを有するゴムラテックスおよび（Ｂ）カゼインに加えて、（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、（Ｄ）エポキシド化合物および（Ｅ）ポリフェノールのうちの１種以上を含む接着剤組成物は、作業性が良好であり、また、有機繊維と被覆ゴム組成物との間の接着性が良好であることが分かる。 From Tables 2 and 3, in addition to (A) a rubber latex having an unsaturated diene and (B) casein, (C) an aqueous compound having a (heat-dissociable blocked) isocyanate group, (D) an epoxide compound and (E). It can be seen that the adhesive composition containing one or more of the polyphenols has good workability and good adhesiveness between the organic fiber and the coated rubber composition.
　本発明によれば、レゾルシンを用いることなく所望の接着性を確保することができ、架橋性に優れるとともに、使用時における作業性を損なうこともない接着剤組成物、これを用いた有機繊維－ゴム複合体およびタイヤを提供できる。従って、本発明は、タイヤ等のゴム物品を製造する産業分野において利用可能である。 According to the present invention, 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.
　１：有機繊維コード
　２：有機繊維用接着剤組成物
　３：浸漬用浴槽（ディッピング槽）
　４：有機繊維用接着剤組成物で被覆された有機繊維コード
　５：絞りロール
　６：乾燥ゾーン
　７：ホットゾーン
　８：ノルマライズゾーン
　１１：不飽和ジエンを有するゴムラテックス
　１２：カゼイン
　１３：（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物によって形成されたウレタン樹脂
　１４：活性化イソシアネート基
　１５：有機繊維コードとの相互作用を得やすい部分
　１６：有機繊維コードに拡散しがたい部分
　２０：ラテックス－カゼイン保護膜効果
　２１：ゴム共加硫接着
　２２：カゼイン－イソシアネート架橋
　２３：活性化イソシアネート架橋
　２４：水性ウレタン－有機繊維界面効果
　３１：有機繊維－ゴム複合体
　３２：有機繊維用接着剤組成物による接着剤層
　３３：被覆ゴム組成物
　４０：芳香環を有するポリイソシアネートと活性水素基を１個以上有するブロック剤との付加生成物からなる水分散性（熱解離性ブロックド）イソシアネート化合物
　４１：芳香族イソシアネート－有機繊維拡散効果
  1: 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) isocyanate compound 41: an addition product of a polyisocyanate having an aromatic ring and a blocking agent having one or more active hydrogen groups. Aromatic isocyanate-organic fiber diffusion effect

Claims (15)

  1. 　（Ａ）不飽和ジエンを有するゴムラテックス、
    　（Ｂ）カゼイン、並びに、
    　下記（Ｃ）～（Ｅ）：
    　（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物、
    　（Ｄ）エポキシド化合物、および、
    　（Ｅ）ポリフェノール
    からなる群から選択される１種以上の化合物を含み、レゾルシンを含まないことを特徴とする有機繊維用接着剤組成物。     (A) Rubber latex with 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) An adhesive composition for organic fibers, which comprises one or more compounds selected from the group consisting of polyphenols and does not contain resorcin.
  2. 　前記（Ｂ）カゼインが、乳由来の等電沈殿カゼインまたはそのアルカリ塩であって、固体、ペースト、溶液、分散液または懸濁液の形態である請求項１記載の有機繊維用接着剤組成物。 The adhesive composition for organic fibers according to claim 1, wherein the casein (B) is an isoelectrically precipitated casein derived from milk or an alkaline salt thereof and is in the form of a solid, a paste, a solution, a dispersion or a suspension. ..
  3. 　前記有機繊維用接着剤組成物中の固形分全体に占める、前記（Ｂ）カゼインの含有量（固形分含有率）が、０．１質量％以上、１５質量％以下である請求項１記載の有機繊維用接着剤組成物。 The first aspect of claim 1, wherein the content (solid content) of (B) casein in the total solid content in the adhesive composition for organic fibers is 0.1% by mass or more and 15% by mass or less. Adhesive composition for organic fibers.
  4. 　前記（Ａ）不飽和ジエンを有するゴムラテックスと前記（Ｂ）カゼインとの混合質量比［（Ａ）：（Ｂ）］（固形分換算）が、１００：０．１から１００：２５の範囲である請求項１または３記載の有機繊維用接着剤組成物。 The mixed mass ratio [(A) :( B)] (solid content conversion) of the rubber latex having (A) unsaturated diene and the (B) casein is in the range of 100: 0.1 to 100: 25. The adhesive composition for an organic fiber according to claim 1 or 3.
  5. 　前記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物が、（Ｃ－１）芳香環を有するポリイソシアネートと活性水素基を１個以上有するブロック剤との付加生成物からなる水分散性（熱解離性ブロックド）イソシアネート化合物である請求項１～４のうちいずれか一項記載の有機繊維用接着剤組成物。 The aqueous compound having the (C) (thermally dissociable blocked) isocyanate group is aqueous dispersion 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. The adhesive composition for an organic fiber according to any one of claims 1 to 4, which is a sex (heat dissociable blocked) isocyanate compound.
  6. 　前記（Ｃ－１）芳香環を有するポリイソシアネートと活性水素基を１個以上有するブロック剤との付加生成物からなる水分散性（熱解離性ブロックド）イソシアネート化合物が、メチレンジフェニルジイソシアネートのブロック体である請求項５記載の有機繊維用接着剤組成物。 The water-dispersible (heat-dissociable blocked) isocyanate compound composed of an addition product of the polyisocyanate having an aromatic ring (C-1) and a blocking agent having one or more active hydrogen groups is a blocked body of methylene diphenyl diisocyanate. The adhesive composition for organic fibers according to claim 5.
  7. 　前記（Ｃ）（熱解離性ブロックド）イソシアネート基を有する水性化合物が、（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物である請求項１～４のうちいずれか一項記載の有機繊維用接着剤組成物。 Any one of claims 1 to 4, wherein the aqueous compound having the (heat dissociative blocked) isocyanate group (C) is the aqueous urethane compound having the (C-2) (heat dissociative blocked) isocyanate group. The adhesive composition for organic fibers according to the above item.
  8. 　前記（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物が、
    　（α）３個以上、５個以下の官能基を有する数平均分子量が２，０００以下の有機ポリイソシアネート化合物、
    　（β）２個以上、４個以下の活性水素基を有する数平均分子量が５，０００以下の化合物、
    　（γ）熱解離性ブロック剤、および、
    　（δ）少なくとも１つの活性水素基と、アニオン性、カチオン性または非イオン性である少なくとも１つの親水基と、を有する化合物、
    を、（α）、（β）、（γ）および（δ）の総和量に対するそれぞれの混合比率が、
    　　（α）については、４０質量％以上、８５質量％以下、
    　　（β）については、５質量％以上、３５質量％以下、
    　　（γ）については、５質量％以上、３５質量％以下、および、
    　　（δ）については、５質量％以上、３５質量％以下、
    になるように混合して、反応させた後の反応生成物であって、かつ、
    　イソシアネート基（－ＮＣＯ）の分子量を４２としたときの、前記反応生成物中における（熱解離性ブロックド）イソシアネート基の構成比率が、０．５質量％以上、１１質量％以下である請求項７記載の有機繊維用接着剤組成物。     The aqueous urethane compound having the (C-2) (heat dissociative blocked) isocyanate group is
    (Α) 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.
    (Β) A compound having 2 or more and 4 or less active hydrogen groups and having a number average molecular weight of 5,000 or less.
    (Γ) Thermal dissociative blocking agent and
    (Δ) A compound having at least one active hydrogen group and at least one hydrophilic group that is anionic, cationic or nonionic.
    The mixing ratio of (α), (β), (γ) and (δ) to the total amount is
    Regarding (α), 40% by mass or more, 85% by mass or less,
    Regarding (β), 5% by mass or more, 35% by mass or less,
    For (γ), 5% by mass or more, 35% by mass or less, and
    Regarding (δ), 5% by mass or more, 35% by mass or less,
    It is a reaction product after mixing and reacting so as to be, and
    The claim that the composition ratio of the (thermally dissociable blocked) isocyanate group in the reaction product when the molecular weight of the isocyanate group (-NCO) is 42 is 0.5% by mass or more and 11% by mass or less. 7. The adhesive composition for organic fibers according to 7.
  9. 　前記（Ｃ－２）（熱解離性ブロックド）イソシアネート基を有する水性ウレタン化合物が、下記一般式（１）：
    Figure JPOXMLDOC01-appb-I000001
    ［式（１）中、
    　Ａは、有機ポリイソシアネート化合物の、活性水素基が脱離した残基、
    　Ｘは、２個以上、４個以下の水酸基を有する、数平均分子量が５，０００以下のポリオール化合物の、活性水素基が脱離した残基、
    　Ｙは、熱解離性ブロック剤の、活性水素基が脱離した残基、
    　Ｚは、少なくとも１つの活性水素基と、少なくとも１つの塩を生成する基または親水性ポリエーテル鎖と、を有する化合物の、活性水素基が脱離した残基、
    　ｎは、２以上４以下の整数、
    　ｐ＋ｍは、２以上４以下の整数（ｍ≧０．２５）
    を表す］で表される請求項７記載の有機繊維用接着剤組成物。     The aqueous urethane compound having the (C-2) (heat dissociative blocked) isocyanate group is described in the following general formula (1):
    Figure JPOXMLDOC01-appb-I000001
    [In equation (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)
    The organic fiber adhesive composition according to claim 7.
  10. 　前記（Ｄ）エポキシド化合物が、１分子中に２個以上のエポキシ基を有する請求項１～９のうちいずれか一項記載の有機繊維用接着剤組成物。 The adhesive composition for organic fibers according to any one of claims 1 to 9, wherein the (D) epoxide compound has two or more epoxy groups in one molecule.
  11. 　前記（Ｄ）エポキシド化合物が、多価アルコール類とエピクロロヒドリンとの反応生成物である請求項１～１０のうちいずれか一項記載の有機繊維用接着剤組成物。 The adhesive composition for organic fibers according to any one of claims 1 to 10, wherein the (D) epoxide compound is a reaction product of polyhydric alcohols and epichlorohydrin.
  12. 　前記（Ｅ）ポリフェノールが、分子内に複数のフェノール性ヒドロキシ基を有する植物由来の化合物である請求項１～１１のうちいずれか一項記載の有機繊維用接着剤組成物。 The adhesive composition for organic fibers according to any one of claims 1 to 11, wherein the (E) polyphenol is a plant-derived compound having a plurality of phenolic hydroxy groups in the molecule.
  13. 　前記（Ｅ）ポリフェノールが、リグニンまたはその誘導体である請求項１～１２のうちいずれか一項記載の有機繊維用接着剤組成物。 The adhesive composition for organic fibers according to any one of claims 1 to 12, wherein the (E) polyphenol is lignin or a derivative thereof.
  14. 　有機繊維とゴムとの複合体であって、該有機繊維が、請求項１～１３のうちいずれか一項記載の有機繊維用接着剤組成物により被覆されていることを特徴とする有機繊維－ゴム複合体。 A composite of an organic fiber and a rubber, wherein the organic fiber is coated with the adhesive composition for an organic fiber according to any one of claims 1 to 13. Rubber composite.
  15. 　請求項１４記載の有機繊維－ゴム複合体を用いたことを特徴とするタイヤ。
          A tire using the organic fiber-rubber composite according to claim 14.
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DE102022121145A1 (en) 2022-08-22 2024-02-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Dispersion, process for its production and use as an adhesive for wood-based materials

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DE102022121145A1 (en) 2022-08-22 2024-02-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Dispersion, process for its production and use as an adhesive for wood-based materials
DE102022121145B4 (en) 2022-08-22 2024-03-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Dispersion, process for its production and use as an adhesive for wood-based materials

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