Classifications

• • 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
  • C09J197/005—Lignin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
  • C08L11/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
  • C08L21/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L7/00—Compositions of natural rubber
  • C08L7/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/02—Copolymers with acrylonitrile
  • C08L9/04—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/10—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
  • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
  • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
  • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
  • C09J161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/395—Isocyanates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
  • D06M15/41—Phenol-aldehyde or phenol-ketone resins
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/687—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing atoms other than phosphorus, silicon, sulfur, nitrogen, oxygen or carbon in the main chain
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C2001/0083—Compositions of the cap ply layers

Definitions

• the present invention relates to an adhesive composition, a rubber-organic fiber cord composite and a tire.
• organic fibers such as polyester fibers have a high initial elastic modulus and excellent thermal dimensional stability. Therefore, in the form of filaments, cords, cables, cord fabrics, canvas, etc., tires, belts, air springs, rubber hoses, etc. It is used as a reinforcing material for rubber articles in the above, and various adhesive compositions have been proposed in order to improve the adhesiveness between these fibers and rubber.
• various adhesive compositions have been proposed in order to improve the adhesiveness between these fibers and rubber.
• an RFL (resorcin formalin latex) adhesive containing resorcin, formalin, rubber latex, etc. is used as the adhesive composition, and the RFL adhesive is thermally cured to secure adhesive strength.
• the adhesive composition is adhered by a technique using a resorcin formalin resin in which resorcin and formalin are initially condensed (Patent Documents 4 and 5) and by pretreating a tire cord made of polyester fiber or the like with an epoxy resin. Techniques for improving power are known.
• Patent Document 6 the amount of resorcin that is generally used in the above-mentioned adhesive composition is required to be reduced from the viewpoint of the environment. Therefore, some adhesive compositions and bonding methods that do not contain resorcin and are environmentally friendly have been proposed (Patent Document 6).
• Another object of the present invention is to provide an adhesive composition that solves the above-mentioned problems of the prior art and can realize excellent adhesiveness even when resorcin is not contained.
• Another object of the present invention is to provide a rubber-organic fiber cord composite and a tire, which have a low environmental load, high productivity, and excellent adhesion between rubber and organic fiber cord. And.
• the gist structure of the present invention that solves the above problems is as follows.
• the adhesive composition of the present invention is characterized by containing polyphenols and formaldehyde.
• the adhesive composition of the present invention can realize excellent adhesiveness even when it does not contain resorcin.
• the polyphenols have three or more hydroxyl groups. In this case, better adhesiveness can be achieved.
• the polyphenols are at least one selected from the group consisting of phloroglucinol, morin, phloroglucinol, lignin, and tannin. In this case as well, better adhesiveness can be achieved.
• the adhesive composition of the present invention preferably further contains an isocyanate compound. In this case as well, better adhesiveness can be achieved.
• the isocyanate compound is a (blocked) isocyanate group-containing aromatic compound. In this case, even better adhesiveness can be realized.
• the adhesive composition of the present invention preferably further contains a rubber latex. In this case as well, better adhesiveness can be achieved.
• the rubber latex is natural rubber (NR), isoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR). ), Butyl halide rubber, acryloni little-butadiene rubber (NBR) and vinylpyridine-styrene-butadiene copolymer rubber (Vp). In this case, even better adhesiveness can be realized.
• NR natural rubber
• IR isoprene rubber
• SBR styrene-butadiene copolymer rubber
• BR butadiene rubber
• EPDM ethylene-propylene-diene rubber
• Vp chloroprene rubber
• NBR acryloni little-butadiene rubber
• Vp vinylpyridine-styrene-butadiene copolymer rubber
• the total content of the polyphenols and the formaldehyde is 5 to 65% by mass in terms of solid content
• the content of the latex is 30 to 95% by mass in terms of solid content
• other components The content is preferably 0 to 65% by mass. In this case, even better adhesiveness can be realized.
• the adhesive composition of the present invention is preferable as an adhesive composition for organic fiber cords because it can improve the adhesiveness between the organic fiber cord and rubber.
• the rubber-organic fiber cord composite of the present invention includes a rubber member and an organic fiber cord. At least a part of the organic fiber cord is coated with the above-mentioned adhesive composition.
• the rubber-organic fiber cord composite of the present invention has excellent adhesiveness between the rubber and the organic fiber cord.
• the tire of the present invention is characterized by including the above-mentioned rubber-organic fiber cord composite.
• the tire of the present invention has excellent adhesion between rubber and an organic fiber cord.
• an adhesive composition capable of achieving excellent adhesiveness even when resorcin is not contained. Further, according to the present invention, it is possible to provide a rubber-organic fiber cord composite and a tire, which have a low environmental load, high productivity, and excellent adhesion between rubber and organic fiber cord. ..
• the adhesive composition of the present invention is characterized by containing polyphenols and formaldehyde. Since resorcin is not used in the adhesive composition of the present invention, the burden on the environment can be reduced. Further, the polyphenols used in place of resorcin form polyphenols / formaldehyde resin together with formaldehyde, and the resin has an adhesive action equivalent to that of resorcin / formaldehyde resin. Therefore, by treating the organic fiber cord with an adhesive composition containing polyphenols and formaldehyde, the adhesiveness between the organic fiber cord and the rubber can be improved. Therefore, the adhesive composition of the present invention can realize excellent adhesiveness even when it does not contain resorcin. Moreover, the adhesive composition of the present invention is preferable as an adhesive composition for an organic fiber cord.
• the adhesive composition contains polyphenols as a resin component. By including polyphenols in the adhesive composition, the adhesiveness of the resin composition can be enhanced.
• the polyphenols are water-soluble polyphenols and are not limited as long as they are polyphenols other than resorcin (resorcinol), and the number of aromatic rings and the number of hydroxyl groups can be appropriately selected. can.
• the polyphenols preferably have two or more hydroxyl groups, and more preferably three or more hydroxyl groups, from the viewpoint of realizing more excellent adhesiveness.
• the polyphenols or the condensate of the polyphenols can be more dissolved in the adhesive composition liquid containing water so that they can be uniformly distributed in the adhesive composition. Excellent adhesiveness can be achieved.
• the polyphenols are polyphenols containing a plurality of (two or more) aromatic rings, two or three hydroxyl groups are present in the ortho, meta or para position, respectively, in those aromatic rings.
• polyphenols having three or more hydroxyl groups examples include phloroglucinol represented by the following structural formula (1) and morin represented by the following structural formula (2) (that is, 2', 4', 3, 5,7-Pentahydroxyflavone), phloroglucinol represented by the following structural formula (3) (that is, 2,4,6,3', 5'-biphenylpentol), and lignin obtained from various plants. And tannins and the like.
• the lignin and tannin are obtained from a plant, but the plant of origin is not particularly limited. Further, the lignin and tannin may be natural products themselves, or may be subjected to various chemical treatments. For example, examples of lignin include dealkali lignin, alkaline lignin, sodium sulfonate lignin and the like. Examples of tannins include plant tannins derived from mimosa and plant tannins derived from quebracho.
• the polyphenols may be used alone or in combination of two or more. Further, it is preferable that the content of polyphenols in the adhesive composition is appropriately adjusted so that the mass ratio as a solid content with formaldehyde, which will be described later, is in a preferable range.
• the adhesive composition contains formaldehyde as a resin component in addition to the above-mentioned polyphenols. By containing formaldehyde in the adhesive composition, high adhesiveness can be realized together with the above-mentioned polyphenols.
• the polyphenols and formaldehyde are condensed, and the mass ratio of the polyphenols to formaldehyde (formaldehyde content / formaldehyde content) is 0.1 or more. It is preferably 3 or less, and more preferably 0.15 or more and 2.5 or less.
• a condensation reaction occurs between the polyphenols and formaldehyde, but if it is within the preferable range of the mass ratio, the hardness and adhesiveness of the resin, which is the product of the polyphenols, will be more suitable.
• the total content of the polyphenols and formaldehyde in the adhesive composition is preferably 5 to 65% by mass, more preferably 5 to 50% by mass, and 5 to 40% by mass. It is more preferable to have. This is because if it is within the preferable range, better adhesiveness can be ensured without deteriorating workability and the like.
• the mass ratio and total content of the polyphenols and formaldehyde are values based on the mass of the dried product (solid content ratio).
• the adhesive composition preferably further contains an isocyanate compound in addition to the above-mentioned polyphenols and formaldehyde.
• an isocyanate compound When the adhesive composition contains an isocyanate compound, the adhesiveness of the adhesive composition can be greatly enhanced by the synergistic effect with polyphenols and formaldehyde.
• the isocyanate compound is a compound having an action of promoting adhesion to a resin material (for example, an organic fiber cord) which is an adherend of an adhesive composition, and has an isocyanate group as a polar functional group. Is.
• the type of the isocyanate compound is not particularly limited, but is preferably a (blocked) isocyanate group-containing aromatic compound from the viewpoint of further improving the adhesiveness.
• the (blocked) isocyanate group-containing aromatic compound is distributed at a position near the interface between the adherend fiber and the adhesive composition, and has an effect of promoting adhesion. Is obtained, and due to this action and effect, the adhesion with the organic fiber cord can be further enhanced.
• the (blocked) isocyanate group-containing aromatic compound is an aromatic compound having a (blocked) isocyanate group.
• (blocked) isocyanate group means a blocked isocyanate group or an isocyanate group, and in addition to the isocyanate group, a blocked isocyanate group generated by reacting with a blocking agent for the isocyanate group and a block for the isocyanate group. It contains an isocyanate group that has not reacted with the agent, or an isocyanate group that is generated by dissociating a blocking agent of a blocked isocyanate group.
• the (blocked) isocyanate group-containing aromatic compound preferably contains a molecular structure in which aromatics are bonded by an alkylene chain, and more preferably contains a molecular structure in which aromatics are methylene-bonded.
• the molecular structure in which aromatics are bonded by an alkylene chain include a molecular structure found in diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, or a condensate of phenols and formaldehyde.
• the (blocked) isocyanate group-containing aromatic compound for example, a compound containing an aromatic polyisocyanate and a heat-dissociable blocking agent, diphenylmethane diisocyanate or an aromatic polyisocyanate is blocked with a heat-dissociable blocking agent.
• a heat-dissociable blocking agent examples include water-dispersible compounds and aqueous urethane compounds containing the above-mentioned components.
• the compound containing the aromatic polyisocyanate and the heat-dissociable blocking agent include a blocked isocyanate compound containing diphenylmethane diisocyanate and a known isocyanate blocking agent.
• a blocked isocyanate compound containing diphenylmethane diisocyanate and a known isocyanate blocking agent As the water-dispersible compound containing a component obtained by blocking the above diphenylmethane diisocyanate or aromatic polyisocyanate with a thermal dissociable blocking agent, diphenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate is used as a known blocking agent for blocking isocyanate groups. Examples of the reaction product blocked in.
• the aqueous urethane compound is an organic polyisocyanate compound ( ⁇ ) containing a molecular structure in which aromatics are bonded by an alkylene chain, preferably a molecular structure in which aromatics are methylene bonded, and a compound having a plurality of active hydrogens ( It is obtained by reacting ⁇ ) with a thermally dissociable blocking agent ( ⁇ ) for an isocyanate group.
• ⁇ organic polyisocyanate compound
• water-soluble means water-soluble or water-dispersible, and “water-soluble” does not necessarily mean completely water-soluble, but is partially water-soluble, or the present invention. It means that the adhesive composition does not undergo phase separation in the aqueous solution of.
• aqueous urethane compound for example, the following general formula (4):
• A indicates a residue from which the active hydrogen of the organic polyisocyanate compound ( ⁇ ) containing a molecular structure in which aromatics are bonded by an alkylene chain is eliminated, and Y indicates a thermally dissociable block to the isocyanate group.
• the active hydrogen of the agent ( ⁇ ) indicates the desorbed residue, Z indicates the residue of the compound ( ⁇ ) desorbed, and X indicates the active hydrogen of the compound ( ⁇ ) having a plurality of active hydrogens. It is a desorbed residue, n is an integer of 2 to 4, and p + m is an integer of 2 to 4 (m ⁇ 0.25). ] Is preferable.
• Examples of the organic polyisocyanate compound ( ⁇ ) containing a molecular structure in which the aromatics are bonded by an alkylene chain include methylene diphenyl polyisocyanate and polymethylene polyphenyl polyisocyanate.
• the compound ( ⁇ ) having a plurality of active hydrogens is preferably a compound having 2 to 4 active hydrogens and having an average molecular weight of 5,000 or less.
• Examples of such compound ( ⁇ ) include (i) polyhydric alcohols having 2 to 4 hydroxyl groups, and (ii) polyhydric amines having 2 to 4 primary and / or secondary amino groups.
• thermally dissociable blocking agent ( ⁇ ) for the isocyanate group is a compound capable of liberating the isocyanate group by heat treatment, and examples thereof include known isocyanate blocking agents.
• the compound ( ⁇ ) is a compound having at least one active hydrogen and anionic and / or nonionic hydrophilic groups.
• Examples of the compound having at least one active hydrogen and an anionic hydrophilic group include aminosulfonic acids such as taurine, N-methyltaurine, N-butyltaurine and sulfanilic acid, and aminocarboxylic acids such as glycine and alanine. Be done.
• aminosulfonic acids such as taurine, N-methyltaurine, N-butyltaurine and sulfanilic acid
• aminocarboxylic acids such as glycine and alanine.
• the content of the isocyanate compound in the adhesive composition is not particularly limited, but is preferably in the range of 5 to 65% by mass from the viewpoint of ensuring more reliable and excellent adhesiveness. More preferably, it is ⁇ 45% by mass.
• the content of the isocyanate compound is a value (solid content ratio) based on the mass of the dried product.
• the adhesive composition may substantially further contain rubber latex in addition to the polyphenols, formaldehyde and isocyanate compounds described above. When the adhesive composition contains rubber latex, the adhesiveness with the rubber member can be further enhanced.
• the rubber latex is obtained by dispersing fine particles of rubber components in water or the like.
• concentration of the rubber component in the rubber latex is preferably in the range of 10 to 60% by mass, more preferably in the range of 20 to 50% by mass.
• the rubber component of the rubber latex is not particularly limited, and in addition to natural rubber (NR), isoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), and ethylene.
• Synthetic rubbers such as -propylene-diene rubber (EPDM), chloroprene rubber (CR), butyl halide rubber, acryloni little-butadiene rubber (NBR), and vinylpyridine-styrene-butadiene copolymer rubber (Vp) can be used. .. These rubber components may be used alone or in a blend of two or more.
• EPDM -propylene-diene rubber
• CR chloroprene rubber
• NBR acryloni little-butadiene rubber
• Vp vinylpyridine-styrene-butadiene copolymer rubber
• the rubber latex is preferably mixed with the polyphenols and formaldehyde before blending with the isocyanate compound. Further, the content of the rubber latex in the adhesive composition is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and 50 to 50% by mass as the solid content (rubber component). It is more preferably 85% by mass.
• the adhesive composition has a total content of the polyphenols and formaldehyde of 5 to 65% by mass in solid content, and a latex content of 30 to 95% by mass in solid content.
• the content of other components is preferably 0 to 65% by mass. In this case, even better adhesiveness can be realized.
• the method for producing the adhesive composition is not particularly limited, but for example, a method of mixing and aging raw materials such as the polyphenols, formaldehyde, and the rubber latex, or a method of mixing and aging the polyphenols and formaldehyde. After that, a method of further adding the rubber latex and aging it can be mentioned.
• the isocyanate compound is contained, the rubber latex can be added and aged, and then the isocyanate compound can be added. Further, it is preferable that the polyphenols and formaldehyde are dissolved in water and used as an aqueous solution.
• the temperature of the water it is preferable to heat the temperature of the water to preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
• the rubber-organic fiber cord composite of the present invention comprises a rubber member and an organic fiber cord, and at least a part of the organic fiber cord is coated with the above-mentioned adhesive composition. ..
• the rubber-organic fiber cord composite of the present invention has excellent adhesiveness between the rubber and the organic fiber cord. Further, since the rubber-organic fiber cord composite uses the adhesive composition, the burden on the environment is small.
• the adhesive composition may cover at least a part of the organic fiber cord, but the adhesiveness between the rubber and the organic fiber cord can be further improved. It is preferable that the adhesive composition is coated on the entire surface of the organic fiber cord.
• the method of coating at least a part of the organic fiber cord with the above-mentioned adhesive composition is not particularly limited, and examples thereof include dipping, coating, and spraying. When the above-mentioned adhesive composition contains a solvent, the solvent can be removed by a drying treatment after coating.
• the material of the organic fiber cord is not particularly limited and can be appropriately selected depending on the intended use.
• the organic fiber cord include a fiber cord made of polyester such as polyethylene terephthalate (PET), a fiber cord made of an aliphatic polyamide such as 6-nylon, 6,6-nylon, and 4,6-nylon, and a fiber made of polyketone.
• PET polyethylene terephthalate
• a fiber cord made of an aliphatic polyamide such as 6-nylon, 6,6-nylon, and 4,6-nylon
• a fiber made of polyketone examples thereof include a cord, a fiber cord made of an aromatic polyamide such as paraphenylene terephthalamide, and a cellulose fiber cord such as rayon.
• the form of the organic fiber cord is not particularly limited, and a monofilament or an organic fiber cord obtained by twisting a plurality of single fiber filaments can be used.
• the average diameter of the single fiber filament is preferably 2 ⁇ m or more, more preferably 15 ⁇ m or more, and preferably 50 ⁇ m or less from the viewpoint of providing sufficiently high reinforcing property to the rubber article. ..
• the form of the organic fiber cord may be a bamboo blind.
• the organic fiber cord may be treated with a solution containing an isocyanate compound and / or an epoxy compound as a pretreatment for coating with the above adhesive composition.
• the treatment mode in which the organic fiber cord is directly treated with the above-mentioned adhesive composition without pretreating the organic fiber cord may be called “1 bath treatment", while the organic fiber cord is pretreated.
• the treatment form in which the organic fiber cord is treated with the above-mentioned adhesive composition after the treatment is sometimes called "two-bath treatment".
• the isocyanate compound used in the solution for pretreatment the isocyanate compound that can be contained in the above-mentioned adhesive composition can be similarly used.
• the isocyanate compound has an action of promoting adhesion of the adhesive composition to the organic fiber cord which is an adherend.
• the content of the isocyanate compound in the solution for pretreatment is not particularly limited, but the ratio of the solid content is preferably more than 5% by mass and 95% by mass or less, preferably 15% by mass or more. , 85% by mass or less is more preferable, and 15% by mass or more and 70% by mass or less is more preferable.
• the content of the isocyanate compound is more than 5% by mass, the strength and chemical resistance of the adhesive layer made of the adhesive composition are improved, and the adhesion and adhesiveness with the organic fiber cord are also improved. Further, when the content of the isocyanate compound is 95% by mass or less, the cohesive fracture resistance of the adhesive layer at high temperature can be sufficiently secured, and the adhesive strength at high temperature is also sufficient.
• epoxy compound used in the above-mentioned pretreatment solution various compounds having at least one epoxy group in one molecule can be used.
• the epoxy compound acts as a cross-linking agent for the above-mentioned adhesive composition, and has excellent adhesiveness, heat resistance, durability, strength, flexibility, electrical insulation and the like.
• the epoxy compound is not particularly limited, but is preferably a compound having two or more epoxy groups in one molecule, and more preferably a compound having four or more epoxy groups.
• the epoxy compound effectively functions as a cross-linking agent due to the epoxy group, and when it has four or more, cross-linking is performed more densely and the epoxy compound is flexible. Gender is also given more.
• the epoxy compound is not particularly limited, but preferably has 10 or less epoxy groups in one molecule. In this case, the crosslink density does not become excessive and the toughness is provided.
• the epoxy compound examples include diethylene glycol / diglycidyl ether, polyethylene / diglycidyl ether, polypropylene glycol / diglycidyl ether, neopentyl glycol / diglycidyl ether, 1,6-hexanediol / diglycidyl ether, and glycerol.
• Polyhydric alcohols such as polyglycidyl ether, trimethylolpropane / polyglycidyl ether, polyglycerol / polyglycidyl ether, pentaerythrithiol / polyglycidyl ether, diglycerol / polyglycidyl ether, sorbitol / polyglycidyl ether, and epichlorohydrin. Reaction products can be mentioned. When these compounds are used as the epoxy compounds, the adhesiveness between the organic fiber cord and the rubber can be further improved.
• the content of the epoxy compound in the above-mentioned pretreatment solution is not particularly limited, but the solid content ratio is preferably in the range of more than 5% by mass and 95% by mass or less, preferably 15% by mass.
• the range of% or more and 85% by mass or less is more preferable, and the range of 15% by mass or more and 50% by mass or less is more preferable. If it is contained in an amount of more than 5% by mass, cross-linking by the epoxy resin is more formed in the adhesive layer made of the adhesive composition, the cohesive breaking resistance and the adhesive force at high temperature are further improved, and the flexibility is also improved. Granted by. Further, if it is 95% by mass or less, the resin cross-linking formed by the adhesive layer is sufficient, and the toughness is further provided.
• the rubber member of the rubber-organic fiber cord composite of the present invention various rubber compositions (raw materials) containing at least a rubber component can be used, and vulcanization obtained by vulcanizing the rubber composition. It is preferable to form the rubber member from rubber.
• the rubber composition contains, for example, a filler such as carbon black or silica, sulfur, peroxide or the like, for a rubber component made of natural rubber or synthetic rubber (butadiene rubber, styrene-butadiene rubber, isoprene rubber, etc.). It can be produced by blending a cross-linking agent, a cross-linking accelerator, or the like, kneading, heating, extruding, or the like.
• the organic fiber cord coated with the adhesive composition is coated with the rubber member. It can be produced by coating with an unvulcanized rubber composition which is a raw material of the above to prepare an unvulcanized rubber-organic fiber cord composite, and then vulcanizing.
• the tire of the present invention is characterized by including the above-mentioned rubber-organic fiber cord composite.
• the tire of the present invention has excellent adhesion between rubber and an organic fiber cord. Further, since the tire uses a rubber-organic fiber cord composite treated with the adhesive composition, the load on the environment is small.
• the rubber-organic fiber cord 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, or using a semi-vulcanized rubber that has undergone a preliminary vulcanization step or the like, depending on the type of tire to be applied. After molding, it may be obtained by further vulcanization.
• an organic fiber cord treated with the above-mentioned adhesive composition is used at any part of the tire, but other members are not particularly limited and known members are used. can do.
• the tire of the present invention is preferably a pneumatic tire, and the gas to be filled in the pneumatic tire is an inert gas such as nitrogen, argon, helium, etc., in addition to normal or oxygen-participated air. Gas can be used.
• An adhesive composition was prepared according to the formulation shown in Table 1. Specifically, 1N aqueous sodium hydroxide solution, polyphenols, and formalin (a solution obtained by diluting a 37% pure formaldehyde aqueous solution manufactured by Kanto Chemical Co., Ltd. 10-fold) were added and dissolved in water, and dissolved at 25 ° C. for 2 A solution containing polyphenols / formaldehyde resin was obtained by stirring for 5 hours. When polyphenols and formalin were added, an aqueous ammonia solution was added as needed.
• the obtained vulcanized product is cooled to room temperature, the cord is dug up from the vulcanized product, and the resistance (N / piece) when the cord is peeled off from the vulcanized product at a rate of 30 cm / min is set to room temperature of 25 ⁇ 1 ° C.
• the measurement was performed at the ambient temperature, and the adhesion state of the rubber was observed. The results are shown in Table 1.
• the evaluation criteria for the score of the rubber adhesion state in Table 1 are as shown in Table 3.
• the pretreated PET cord is treated with the above adhesive composition (second bath), and then unvulcanized rubber containing a natural rubber, a rubber component composed of a styrene-butadiene copolymer, carbon black, and a cross-linking agent. It was embedded in the composition to prepare a rubber-organic fiber cord composite, which was further vulcanized at 160 ° C. for 20 minutes under a pressure of 20 kgf / cm 2.
• the obtained vulcanized product is cooled to room temperature, the cord is dug up from the vulcanized product, and the resistance (N / piece) when the cord is peeled off from the vulcanized product at a rate of 30 cm / min is set to room temperature of 25 ⁇ 1 ° C.
• the measurement was performed at the ambient temperature, and the adhesion state of the rubber was observed. The results are shown in Table 1.
• the evaluation criteria for the score of the rubber adhesion state in Table 1 are as shown in Table 3.
• AB indicates that it was between A and B.
• an adhesive composition capable of achieving excellent adhesiveness even when resorcin is not contained. Further, according to the present invention, it is possible to provide a rubber-organic fiber cord composite and a tire having a small environmental load and excellent adhesiveness between the rubber and the organic fiber cord.

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• 2021
  • 2021-03-10 WO PCT/JP2021/009653 patent/WO2021182542A1/ja not_active Ceased
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  • 2021-03-10 EP EP21767101.5A patent/EP4119631A4/en active Pending

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