Classifications

• • 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
  • D06M15/03—Polysaccharides 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
  • 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
  • D06M13/35—Heterocyclic compounds
  • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
• • 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
  • D06M15/55—Epoxy resins
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
• • D—TEXTILES; PAPER
  • 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
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/32—Polyesters
• • 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
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

• the present invention relates to a novel adhesive treatment agent and synthetic fiber cord for rubber reinforcement that are advantageous in reducing environmental impact.
• Synthetic fibers such as nylon fibers, polyester fibers, and aromatic polyamide fibers are widely used as reinforcing materials for rubber products such as tires, hoses, and belts.
• RFL resorcinol-formalin-latex
• adhesives containing resorcinol, formalin and rubber latex have hitherto been widely used as means for bonding these synthetic fibers of rubber products to rubber compositions.
• both resorcin and formalin are deleterious substances, have a high environmental load, and are harmful to health.
• adhesive agents for rubber and fibers typified by RFL adhesives
• storage stability such as changes in adhesive strength and physical properties.
• Patent Documents 1 to 6 are disclosed as technologies for addressing the above problem.
• Patent Document 1 discloses an adhesive composition for organic fiber cords containing a urethane resin having a thermally dissociable blocked isocyanate group, an epoxy compound, a polymer having an oxazoline group, a basic catalyst having a number average molecular weight of 1,000 to 75,000, and rubber latex. object is disclosed.
• Patent Document 2 discloses a processing method in which a fabric reinforcing member is immersed in a bath containing a polycarboxylic acid, a base, an epoxy compound, a polyisocyanate compound, and VP latex.
• Patent Document 3 discloses a water-based adhesive composition containing a thermosetting resin having a specific functional group and an unsaturated elastomer latex.
• Patent Document 4 at least one component selected from the group consisting of polyphenols, chlorophenol resins and lignin resins, and at least one selected from water-soluble polymers other than the above components or water-dispersible polymers other than the above components Organic fiber adhesives containing one component are disclosed.
• Patent Document 5 discloses a water-based adhesive composition containing a specific blocked isocyanate oligomer having a functionality of 3 or more, a latex, a polyacrylate or a lignin compound, and an additive.
• Patent Document 6 discloses a method for producing an adhesive composition with good storage stability, which comprises aging in a state containing resorcin and formaldehyde and not containing an alkali catalyst, and then adding rubber latex to form a mixed solution. ing.
• JP 2013-64037 A Japanese Patent Publication No. 2020-525622 Japanese Patent Publication No. 2019-518087 WO2018/003572 U.S. Publication No. 2020/0024416 JP 2013-10909 A
• Patent Documents 1 and 5 initial adhesive strength and heat-resistant adhesive strength are exhibited at the same level as conventional RFL, but fatigue resistance in rubber is not sufficient. According to Patent Literatures 2, 3 and 4, the initial adhesive strength is as high as the conventional RFL, but the heat-resistant adhesive strength and fatigue resistance in rubber are insufficient. Moreover, Patent Documents 1 and 2 use a fossil fuel-derived compound as a substitute for resorcinol/formalin, which is somewhat disadvantageous in terms of reducing the environmental load. According to Patent Document 6, although the storage stability of the adhesive treatment agent is improved, it uses a conventional RFL adhesive, which has the problem of a large environmental load. In addition, in all of Patent Documents 1 to 6, the problem of resin solidification occurring in the dipping process remains.
• the present invention has been made as a result of studies aimed at solving the problems in the conventional technology described above.
• An object of the present invention is to provide a novel adhesive treatment agent that does not contain resorcin and formalin and uses raw materials that are advantageous in reducing the environmental load, and a synthetic fiber cord for rubber reinforcement using the same, which has an initial value equal to or higher than that of the conventional RFL.
• Synthetic fiber cord for rubber reinforcement that exhibits adhesive strength, exhibits less adhesion deterioration under high temperature conditions for a long period of time when embedded in rubber, and suppresses deterioration in strength when subjected to repeated stretching and compression in rubber. is to provide Furthermore, the present invention provides an adhesive treatment agent for rubber and fiber and a rubber-reinforcing synthetic fiber cord which have good storage stability of the adhesive treatment agent, can suppress the generation of resin coagulation in the dipping step, and have good productivity.
• the present invention employs the following means in order to solve such problems.
• the rubber/fiber adhesive treatment agent according to (1) above which has a maximum point strength of 0.2 MPa to 1.6 MPa and a maximum point elongation of 2% to 120%.
• the rate of change V 30 /V 0 of the liquid viscosity (V 30 (mPa ⁇ s) after 30 days) compared to the liquid viscosity (V 0 (mPa ⁇ s)) after preparation of the adhesive agent is 90.
• Rubber-reinforcing synthetic fiber cords obtained by adhering the rubber/fiber adhesive treatment agent according to any one of the above (1) to (6) to synthetic fibers and subjecting them to heat treatment.
• a novel adhesive treatment agent and a synthetic fiber cord for reinforcing rubber which do not contain resorcin and formalin and use raw materials that are advantageous in reducing the environmental load, and exhibit an initial adhesive strength equal to or greater than that of conventional RFL.
• the rubber/fiber adhesive treatment agent of the present invention is capable of exhibiting adhesiveness to rubber when synthetic fibers are treated.
• the lignin derivative (A) used in the present invention is chemically treated lignin present in trees, which are biomass.
• Such materials include, for example, kraft lignin obtained from kraft pulp effluent, lignin sulfonic acid or lignin sulfonate obtained from sulfite pulp effluent, and the like in the papermaking industry process using wood as a raw material.
• Lignin sulfonic acid is obtained by introducing a sulfone group into the side chain of the phenylpropane structure of lignin.
• Examples of ligninsulfonates include sodium ligninsulfonate, magnesium ligninsulfonate, and calcium ligninsulfonate. In the present invention, these can be used singly or in combination, but sodium lignosulfonate is most preferably used from the viewpoint of adhesive strength.
• the lignin derivative (A) used in the present invention must have a number average molecular weight of 10000 to 60000 and a weight average molecular weight of 80000 to 130000, preferably a number average molecular weight of 20000 to 50000 and a weight average It is preferable that the molecular weight is 90,000 to 120,000. If the number-average molecular weight and weight-average molecular weight exceed the upper limit of this range, the fatigue resistance will be insufficient, the storage stability of the adhesive treatment agent will be deteriorated, and many coagulates will occur during the dipping process, making continuous production difficult.
• the number-average molecular weight and weight-average molecular weight are less than the lower limits of these ranges, the initial adhesive strength with rubber and fatigue resistance are unfavorably lowered.
• the weight average molecular weight (Mw)/number average molecular weight (Mn) is preferably 2.5 to 5.0, more preferably 2.8 to 4.7. Outside this range, the adhesive strength and fatigue resistance may be insufficient.
• the number average molecular weight and weight average molecular weight in the present invention refer to values measured by the methods described in Examples.
• the water-soluble or water-dispersible cross-linking agent (B) used in the present invention is a compound having a functional group capable of reacting with other compounds by heating, and is water-soluble or emulsion-type water-dispersible. Specifically, it preferably contains at least one compound selected from the group consisting of oxazoline group-containing compounds, epoxy compounds, and blocked isocyanate compounds.
• An oxazoline group-containing compound refers to a compound containing an oxazoline group (preferably a 2-oxazoline group) at the terminal or side chain of a substance having a general organic compound or organic polymer and/or oligomer as a main skeleton.
• an oxazoline group preferably a 2-oxazoline group
• One or two or more oxazoline groups can be present in one molecule, but it is more preferable to have many oxazoline groups, which are reactive functional groups, in order to improve adhesion performance.
• a hydrocarbon chain, an ethylene glycol chain, a bisphenol such as bisphenol A, or an initial polymer such as a phenol resin, a novolac resin, or a resol resin is used.
• substances containing aromatic or heterocyclic rings are also used.
• these monomers include styrene, styrene derivatives, acrylonitrile, methacrylic acid esters, methacrylic acid, ethylene, butadiene, acrylamide, etc. They are used as single polymers and/or oligomers and also as copolymers. . A mixture thereof can also be used.
• the oxazoline group-containing compound may be in the form of a liquid, a melt, a solid, a solution in water or an organic solvent capable of dissolving them, or a suspension dispersed in water (emulsion particles, latex particles, etc.).
• a method of emulsifying or dissolving such a compound as it is or, if necessary, dissolving it in a small amount of solvent using a known emulsifier such as sodium alkylbenzenesulfonate, dioctylsulfosuccinate sodium salt, nonylphenol ethylene oxide adduct, etc. may be used.
• An epoxy compound has two or more epoxy groups in one molecule.
• Compounds having two or more epoxy groups in the molecule include, for example, glycidyl ether type epoxy resins obtained from compounds having hydroxyl groups in the molecule, glycidyl amine type epoxy resins obtained from compounds having amino groups in the molecule, A glycidyl ester type epoxy resin obtained from a compound having a carboxyl group in the molecule, a cycloaliphatic epoxy resin obtained from a compound having an unsaturated bond in the molecule, a heterocyclic epoxy resin such as triglycidyl isocyanurate, or selected from these It is an epoxy resin in which two or more types are mixed in the molecule.
• glycidyl ether-type epoxy resins include bisphenol A-type epoxy resins obtained by reacting bisphenol A with halogen-containing epoxides such as epichlorohydrin, and bisphenol F obtained by reacting bisphenol F with halogen-containing epoxides.
• Biphenyl-type epoxy resins obtained by reaction of biphenyl and the halogen-containing epoxides Resorcinol-type epoxy resins obtained by the reaction of resorcinol and the halogen-containing epoxides, Bisphenol S and the halogen-containing epoxides bisphenol S-type epoxy resins obtained by reaction with bisphenol S-type epoxy resins, polyethylene glycol-type epoxy resins that are reaction products of polyhydric alcohols and halogen-containing epoxides, polypropylene glycol-type epoxy resins, bis-(3,4-epoxy -6-methyl-dicyclohexylmethyl)adipate, epoxy resins obtained by oxidizing unsaturated bond moieties such as 3,4-epoxycyclohexene epoxide, other naphthalene type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, and halogen- or alkyl-substituted
• the blocked isocyanate compound used in the present invention is a compound that can generate an active isocyanate compound by liberating the blocking agent by heating.
• Blocked isocyanate compounds include polyisocyanate compounds having a skeleton such as tolylene diisocyanate (TDI), metaphenylene diisocyanate (MDI), diphenylmethane diisocyanate (HDI), hexamethyline diisocyanate, and triphenylmethane triisocyanate, and phenol and cresol.
• phenols such as resorcinol
• lactams such as ⁇ -caprolactam and valerolactam
• reaction products with blocking agents such as oximes such as acetoxime, methyl ethyl ketoxime and cyclohexane oxime.
• HDI blocked isocyanate which is a reaction product of hexamethylene diisocyanate and a blocking agent
• MDI which is a reaction product of diphenylmethane diisocyanate and an oxime blocking agent
• Selection from among the oxime blocked isocyanates is most preferred for obtaining good adhesion and fatigue resistance.
• Diphenylmethane diisocyanate (MDI) can be selected from 2,2′-MDI, 2,4′-MDI, 4,4′-MDI, but the monomeric MDI of 4-4′-MDI is the adhesive and Most preferred from the viewpoint of fatigue resistance.
• polymeric MDI having a trifunctional isocyanate group is not preferable because adhesive strength and fatigue resistance may decrease.
• the dissociation temperature of the blocking agent for HDI-based blocked isocyanate or MDI-based oxime-blocked isocyanate is preferably 100 to 160°C. When the dissociation temperature is within this range, the reactivity at the time of heat treatment is good, and a higher adhesive force can be expressed, which is preferable.
• Rubber latex (C) that can be used in the present invention includes, for example, natural rubber latex, butadiene rubber latex, styrene-butadiene-rubber latex, vinylpyridine-styrene-butadiene rubber latex, nitrile rubber latex, hydrogenated nitrile rubber latex, and chloroprene rubber. Latex, chlorosulfonated rubber latex, ethylene/propylene/diene rubber latex and the like can be mentioned, and these can be used alone or in combination.
• the present invention does not contain resorcinol-formaldehyde resin.
• the resorcinol-formaldehyde resin is a compound obtained by reacting resorcinol and formaldehyde. For example, by mixing resorcinol and formaldehyde in an alkaline aqueous solution containing an alkaline compound such as sodium hydroxide and allowing the mixture to stand at room temperature for several hours, the condensation reaction between resorcinol and formaldehyde proceeds and a resorcinol-formaldehyde resin is obtained. .
• the adhesive agent that can be used in the present invention includes, if necessary, a surfactant within a range that does not interfere with the object and effect of the present invention.
• a surfactant within a range that does not interfere with the object and effect of the present invention.
• antifoaming agents, vulcanization modifiers, antioxidants and pH modifiers may be added.
• the content of the lignin derivative (A) is preferably 5 to 50% by weight, more preferably 7% by weight, when the total solid content contained in the adhesive agent is 100% by weight. ⁇ 45% by weight, more preferably 10-40% by weight. If it is less than 5% by weight or more than 50% by weight, the adhesive strength and fatigue resistance may be insufficient.
• total solid content as used herein means the components of the adhesive treatment agent excluding the solvent.
• the adhesion treatment agent of the present invention preferably has a maximum point strength of 0.2 MPa to 1.6 MPa, more preferably 0.3 MPa to 1.4 MPa, when the adhesion treatment agent is used as a dry film. More preferably, it should be 0.5 MPa to 1.4 MPa. If the maximum point strength is less than 0.2 MPa, the adhesive strength may be insufficient, and if it exceeds 1.6 MPa, the fatigue resistance may deteriorate. Also, the maximum point elongation of the dry film is preferably 2% to 120%, more preferably 4% to 100%, still more preferably 20% to 100%. If the maximum point elongation is less than 2%, fatigue resistance may deteriorate, and if it exceeds 120%, adhesion may be insufficient.
• the method for adjusting the dry film and the method for measuring the maximum point strength and maximum point elongation are according to the methods described in the Examples section. However, if it is difficult to use this method, an equivalent method can be used.
• the maximum point strength and maximum point elongation of the dry film of the adhesive agent can be adjusted by the chemical species and mixing ratio contained in the adhesive agent.
• the maximum point strength can be adjusted to be high by increasing the content of the water-soluble or water-dispersible cross-linking agent (B) contained in the adhesive treatment agent.
• B water-soluble or water-dispersible cross-linking agent
• C rubber latex
• the adhesive agent of the present invention preferably has a liquid viscosity (V 0 (mPa ⁇ s)) after preparation of 1.0 to 3.0 mPa ⁇ s, more preferably 1.1 to 2.7 mPa ⁇ s. is s. If the liquid viscosity is less than 1.0, the adhesion of the adhesive treatment agent to the synthetic fiber may be insufficient, resulting in a decrease in adhesive strength. becomes excessive, and continuous production may become difficult due to deterioration in adhesive strength, generation of coagulum in the dipping process, and the like.
• V 0 (mPa ⁇ s) liquid viscosity after preparation of 1.0 to 3.0 mPa ⁇ s, more preferably 1.1 to 2.7 mPa ⁇ s. is s. If the liquid viscosity is less than 1.0, the adhesion of the adhesive treatment agent to the synthetic fiber may be insufficient, resulting in a decrease in adhesive strength. becomes excessive, and continuous production may become difficult due to deterioration in adhesive strength, generation of coagulum
• the change rate V 30 /V 0 of the liquid viscosity (V 30 (mPa s)) after 30 days compared to the liquid viscosity (V 0 (mPa s)) after preparation is 90 to 120%. More preferably, the rate of change V 30 /V 0 is 92 to 110%, still more preferably 95 to 110%. A specific method for measuring the viscosity will be described later, but the viscosity change rate in the same test is utilized in the present invention as a measure of the storage stability of the adhesive treatment agent.
• the viscosity change rate is less than 90% or more than 120%, the amount of the adhesive agent adhering to the synthetic fiber changes in the dipping process due to the change in the viscosity of the adhesive agent. Coagulation may occur, making continuous production difficult.
• the method of adjusting the liquid viscosity of the adhesive treatment agent within the specified range of the present invention is, for example, the selection and blending of the lignin derivative (A), the water-soluble or water-dispersible cross-linking agent (B), and the rubber latex (C) to be used. It can be adjusted by optimizing the ratio. Further, a surfactant may be additionally added as appropriate. Examples of surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, and alkylbenzenesulfonates.
• the adhesive agent of the present invention has a solid content dissolved or dispersed in water, and the total solid content concentration is preferably 5 to 25% by weight, more preferably 10 to 20% by weight, and still more preferably 12% by weight. A content of up to 18% by weight is preferable. Outside this range, the adhesive strength may be lowered. Outside this range, it may not be possible to impart a sufficient amount of solids to the fibers, or cohesive failure at the adhesive solids may occur, which may lead to a decrease in adhesion. .
• the rubber-reinforcing synthetic fiber cord of the present invention which can be suitably used for reinforcing rubber, is obtained by treating synthetic fibers with the rubber/fiber adhesive treatment agent described above.
• treated means a state in which a drying treatment or heat treatment is performed after applying an adhesive treatment agent to synthetic fibers.
• volatile matter contained in the adhesive treatment agent such as solvents such as water, is distilled off. Reaction with isocyanate groups occurs. That is, the synthetic fibers treated with the adhesive treatment agent are in a state in which the solid content in the adhesive treatment agent is adhered to or bonded to the synthetic fibers without being chemically denatured or denatured.
• the adhesive agent of the present invention contains at least a lignin derivative (A), a water-soluble or water-dispersible cross-linking agent (B), and a rubber latex (C) in the same bath (one bath).
• the adhesion amount of the adhesive treatment agent to the synthetic fibers is preferably 1 to 15 parts by weight, more preferably 1.5 parts by weight, based on the solid content of the adhesive treatment agent per 100 parts by weight of the synthetic fibers. ⁇ 10 parts by weight is preferred. Outside this range, the adhesive strength may be lowered.
• the synthetic fibers that can be used in the present invention are preferably in the form of multifilaments.
• materials constituting synthetic fibers include nylon fibers, polyester fibers, aramid fibers, polyvinyl alcohol fibers, and the like. From the standpoint of durability and industrial productivity, it is particularly preferred to include at least one selected from polyester fibers, nylon fibers, and aramid fibers. At least one fiber selected from polyester fiber, nylon fiber, and aramid fiber accounts for 60% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more when the weight of the entire synthetic fiber is 100% by weight. preferably occupy.
• polyester fiber examples include fibers made of polyethylene terephthalate, polyethylene naphthalate, etc. It is preferable that the polyester is a fiber obtained by melt-spinning and drawing a polyester containing terephthalic acid as a main bifunctional carboxylic acid and ethylene glycol as a glycol component. Desirably, terephthalic acid is partially or wholly replaced with 2,6-naphthalenedicarboxylic acid, 4,4-dicarboxyphenoxyethane, isocyanate group, etc., and ethylene glycol is partially or wholly diethylene glycol, propylene glycol, butanediol. It is also possible to use fibers made of polyester replaced with, for example.
• the above polyester may be copolymerized with a trifunctional compound such as trimesic acid, trimellitic acid, boric acid, phosphoric acid, glycerin, and trimethylolpropane, as long as the amount is small.
• a trifunctional compound such as trimesic acid, trimellitic acid, boric acid, phosphoric acid, glycerin, and trimethylolpropane, as long as the amount is small.
• polyester fibers may be modified with various modifiers, for example, terminal carboxyl group blocking agents such as carbodiimide compounds, epoxy compounds, isocyanate compounds, and oxazoline compounds.
• terminal carboxyl group blocking agents such as carbodiimide compounds, epoxy compounds, isocyanate compounds, and oxazoline compounds.
• polyepoxide compounds include compounds containing at least two or more epoxy groups per molecule in an amount of 0.1 g equivalent or more per 100 g of the compound.
• reaction products of polyhydric alcohols such as pentaerythritol, ethylene glycol, polyethylene glycol, propylene glycol, glycerol and sorbitol and halogen-containing epoxides such as epichlorohydrin, peroxides, unsaturated with hydrogen peroxide, etc.
• polyepoxide compounds obtained by oxidizing compounds such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate, phenol novolac type, Aromatic polyepoxides such as hydroquinone type, biphenyl type, bisphenol S type, brominated novolac type, xylene-modified novolac type, phenolglyoxal type, trisoxyphenylmethane type, trisphenol PA type, bisphenol type polyepoxides, and the like. Particularly preferred are sorbitol glycidyl ether type and cresol novolac type polyepoxides.
• polyepoxide compounds are usually used as emulsions and solutions. That is, the above compound is dissolved in a solvent and used as a solution, or emulsified with a common emulsifier such as sodium alkylbenzenesulfonate, dioctylsulfosuccinate sodium salt, nonylphenol ethylene oxide adduct, etc., and used as an emulsion.
• a common emulsifier such as sodium alkylbenzenesulfonate, dioctylsulfosuccinate sodium salt, nonylphenol ethylene oxide adduct, etc.
• the polyepoxide compound is applied together with the spinning oil in the synthetic fiber spinning process.
• the adhered amount of the polyepoxide compound at this time is preferably in the range of 0.1 to 5% by weight. If the adhesion amount of the polyepoxide compound is within the above range, the effect of the polyepoxide compound is sufficiently exhibited, and satisfactory adhesiveness is obtained between the synthetic fiber and the rubber. In addition, within the above range, the fiber does not become too hard, and the strength is less likely to decrease in the yarn twisting step described later.
• nylon fiber examples include fibers made of nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, etc.
• high molecular weight nylon 66 having a sulfuric acid relative viscosity of 3.0 or more, more preferably 3.5 or more is preferable, and can contain copper compounds, conventionally known inorganic and organic copper salts, and simple copper metals.
• copper compounds conventionally known inorganic and organic copper salts, and simple copper metals.
• other heat-resistant agents such as amine compounds, mercapto compounds, phosphorus compounds, and hindered phenol compounds may be contained.
• a polymer with a high degree of polymerization is used in order to obtain fibers with high strength and high toughness, and fibers with a sulfuric acid relative viscosity of 3.0 to 5.0 are preferably used.
• the above-mentioned aramid fiber is not particularly limited as long as it is a fiber having at least one divalent aromatic group that may be usually substituted in the repeating unit of the polymer forming the fiber and at least one amide bond. , wholly aromatic polyamide fiber, or known aramid fiber.
• "optionally substituted divalent aromatic group” means a divalent aromatic group optionally having one or more identical or different substituents.
• Aramid fibers include para-aramid fibers and meta-aramid fibers, but in the present invention, para-aramid fibers having excellent tensile strength can be preferably used.
• para-aramid fibers include poly-paraphenylene terephthalamide fibers (manufactured by DuPont of the United States, DuPont-Toray, product name "Kevlar” (registered trademark)), copolyparaphenylene-3,4'-oxydiphenylene Phenylene terephthalamide fiber (manufactured by Teijin Limited, product name “Technora” (registered trademark)) and the like can be mentioned.
• Synthetic fibers used in the present invention are not subject to restrictions such as fineness, number of filaments, cross-sectional shape, etc., but usually have a total fineness of 200 to 5000 dtex, 30 to 1000 filaments, and a circular cross-section yarn. ⁇ 500 filament, circular section yarn is preferred. If the total fineness is less than 200 dtex, the strength of the cord may be insufficient. On the other hand, if the number of filaments is less than 30 filaments, the cord may become hard and may be difficult to handle.
• the synthetic fiber cord of the present invention is obtained by twisting the above synthetic fibers into a twisted cord, and then dipping the twisted cord with the adhesive treatment agent of the present invention after weaving the twisted cord as it is or in a blind shape. It can be obtained by heat treatment.
• twisted yarn cords used for carcass tire cords are ply-twisted in the S or Z direction, and then two or three ply-twisted cords are put together and usually the same number of ply-twisted in the direction opposite to the ply-twisted.
• a twisted yarn cord can be used.
• the twisted yarn cord is used as warp, and cotton yarn is used as weft, or organic fiber is covered with cotton yarn to make weft, and the fabric is woven in a sudare pattern to form a woven cloth, and then the woven cloth is dipped in an adhesive agent.
• a dip fabric is obtained by heat treatment.
• a twisted yarn cord is formed by first twisting, or two or three of these first twisted cords are combined and usually the same number of ply twists are applied in the opposite direction to the first twist.
• a twisted yarn cord is obtained by ply twisting, and the twisted yarn cord is dipped in an adhesive treatment agent and heat-treated to obtain a dipped cord.
• the synthetic fiber cords treated with the adhesive treatment agent of the present invention include both the above dipped cords and dipped cords.
• the rubber-reinforcing synthetic fiber cord of the present invention is pre-coated before the synthetic fiber is treated with the adhesion treatment agent (adhesion treatment agent containing at least component (A), component (B) and component (C)). It may be treated with an agent.
• adhesion treatment agent containing at least component (A), component (B) and component (C)
• the precoating agent contains at least an epoxy compound, and the concentration of the total solid content in the precoating agent is preferably 0.1 to 6%. More preferably, it contains at least an epoxy compound and a blocked isocyanate compound, (solid content weight of blocked isocyanate compound) ⁇ (solid content weight of epoxy compound) is 3 or less, and the total solid content in the precoat agent is It is preferable that the concentration is 0.1 to 6%. Outside this range, the adhesive strength may decrease.
• the amount of the precoating agent attached to the synthetic fibers is preferably such that the solid weight of the precoating agent per 100 parts by weight of the synthetic fibers is 0.1 to 3 parts by weight. Outside this range, the adhesive strength may be lowered.
• the rubber/fiber adhesive treatment agent of the present invention characterized by the above comprises a novel adhesive treatment agent that does not contain resorcin and formalin and uses raw materials that are advantageous in reducing environmental load.
• the fiber cord exhibits an initial adhesive strength equal to or greater than that of conventional RFL, less adhesion deterioration under high temperature for a long time when embedded in rubber, and strength deterioration when subjected to repeated stretching and compression in rubber. is suppressed, and can be suitably used for rubber reinforcement. Further, it is possible to provide an adhesive treatment agent for rubber/fiber and a synthetic fiber cord for rubber reinforcement, which have good storage stability of the adhesive treatment agent, can suppress the generation of resin coagulation in the dipping step, and have good productivity.
• the rubber-reinforcing synthetic fiber cord of the present invention is obtained by applying the rubber/fiber adhesive treatment agent described above to synthetic fibers and then heat-treating the synthetic fibers.
• the rubber-reinforcing synthetic fiber cord of the present invention can be used, for example, for reinforcing rubber products such as tires, belts and hoses. Performance equal to or greater than that used can be expressed.
• An example of the method for producing a rubber-reinforcing synthetic fiber cord of the present invention includes at least a lignin derivative (A), a water-soluble or water-dispersible cross-linking agent (B) and a rubber latex (C), and a resorcin-formaldehyde resin. is applied to synthetic fibers in the same bath, followed by heat treatment.
• the synthetic fibers may be in the form of twisted cords or woven fabrics, and the twisted cords or woven fabrics are dipped in an adhesive treatment agent in a dip bath bath, followed by dehydration at a temperature of preferably 100 to 150°C. A method of drying followed by heat treatment at 200-255° C. is preferred.
• Preferred embodiments of the lignin derivative (A), the water-soluble or water-dispersible cross-linking agent (B) and the rubber latex (C) are those described above.
• dipping means applying an adhesive treatment agent to the twisted cords or silk fabric by running the twisted yarn cords or silk fabric in a dipping tank in which a roller is installed and which is filled with an adhesive treatment agent.
• the heat treatment refers to heating the twisted cord or the textile by running the twisted yarn cord or the textile in an oven in which rollers are installed and which can be set to a predetermined temperature.
• a dipping machine for performing such dipping and heat treatment is commercially available from, for example, Ritzler.
• any method for attaching the adhesive treatment agent to the synthetic fibers any method such as application by spraying the adhesive treatment agent from a nozzle in addition to the dipping treatment can be adopted.
• means such as squeezing with a pressure contact roller, scraping off with a scraper, blowing off with air blowing and suction may be used.
• the synthetic fiber cord is brought into sliding contact with the edge to apply a softening treatment to obtain an arbitrary cord stiffness.
• the adhesive treatment agent (adhesion treatment agent containing at least component (A), component (B) and component (C)) is applied to the synthetic fiber, and then heat treated.
• a pre-coating agent may be attached to the surface and heat-treated.
• the precoating agent contains at least an epoxy compound, and the concentration of the total solid content in the precoating agent is preferably 0.1 to 6%. More preferably, it contains at least an epoxy compound and a blocked isocyanate compound, (solid content weight of blocked isocyanate compound) ⁇ (solid content weight of epoxy compound) is 3 or less, and the total solid content in the precoat agent is It is preferable that the concentration is 0.1 to 6%. Outside this range, the adhesive strength may decrease.
• the amount of the precoating agent attached to the synthetic fibers is preferably such that the solid weight of the precoating agent per 100 parts by weight of the synthetic fibers is 0.1 to 3 parts by weight. Outside this range, the adhesive strength may be lowered.
• the same dipping method as the above method can be adopted. That is, a synthetic fiber twisted cord or woven cloth is dipped in a precoating agent in a dip bath bath, followed by drying the moisture at a temperature of preferably 100 to 150°C, followed by heat treatment at 200 to 255°C. is preferred.
• the same methods as described above can be employed for controlling the amount of solid matter adhered and for the softening treatment.
• the adhesive agent for rubber and fiber and the synthetic fiber cord for rubber reinforcement of the present invention are free from resorcin and formalin, and are advantageous novel adhesive agents using biomass-derived raw materials for reducing environmental load. As a result, it exhibits an initial adhesive strength equal to or greater than that of conventional RFL, less adhesion deterioration under high temperature for a long time when embedded in rubber, and suppresses strength deterioration when subjected to repeated stretching and compression in rubber. and can be suitably used for rubber reinforcement. Further, it is possible to provide an adhesive treatment agent for rubber/fiber and a synthetic fiber cord for rubber reinforcement, which have good storage stability of the adhesive treatment agent, can suppress the generation of resin coagulation in the dipping step, and have good productivity.
• Amount of Adhesive Treating Agent The amount of adhesive applied to the synthetic fiber cord for rubber reinforcement was determined according to the dip pickup mass method of JIS L1017 (2002).
• the heat-resistant adhesive strength was measured by embedding a synthetic fiber cord for rubber reinforcement in unvulcanized rubber in accordance with the 3.1T test (A method) of Annex 1 of JIS L1017 (2002), 170°C for 70 minutes. , 50 kg/cm 2 press vulcanization was performed, then allowed to cool, the synthetic fiber cord was pulled out from the rubber block at a speed of 300 mm/min, the load required for pulling out was determined for each sample, and arithmetic was performed on 10 samples. The average value was defined as the heat-resistant adhesive strength.
• the breaking strength before the fatigue test indicates the breaking strength measured by preparing the rubber composite as described above, taking out the synthetic fiber cord from the rubber and conducting a tensile test before conducting the fatigue test. That is, the fatigue resistance in rubber (retention rate) (%) is calculated by (breaking strength of the cord removed from the rubber after the fatigue test)/(breaking strength of the cord removed from the rubber before the fatigue test) x 100. The breaking strength of the cord taken out from the rubber before the fatigue test is 100% retention.
• the composition of the unvulcanized rubber compound used for the measurement of initial adhesive strength, heat-resistant adhesive strength, and fatigue resistance in rubber is as follows.
• liquid viscosity after liquid preparation refers to the liquid viscosity obtained by measuring from immediately after liquid preparation to 1 hour after liquid preparation.
• the adhesive treatment agent sample was allowed to stand in a constant temperature bath at 25 ⁇ 0.5° C., and 30 days after preparation, the liquid viscosity (V 30 (mPa ⁇ s)) was measured in the same manner, and the rate of change V 30 /V 0 (%) was calculated.
• the maximum point elongation (%) was calculated by elongation (mm) of the sample at the point where the strength reaches the maximum value/initial test length (50 mm) x 100.
• the elongation is 0 mm before the tensile test, the elongation is 0%, and when the elongation after the tensile test is 50 mm, the elongation is 100%.
• Measuring device Shimadzu Corporation Column used: TSKgel GMPW XL 1 piece, G3000PW XL 1 piece ( ⁇ 7.8 mm ⁇ 30 cm, manufactured by Tosoh) Solvent: 0.1 M ammonia buffer (pH 11)/methanol (4/1, v/v) Standard material: Tosoh and Agilent monodisperse polyethylene oxide, polyethylene glycol Detector: UV detector (Shimadzu SPD-M20A).
• Examples 1 to 10, Comparative Examples 1 to 6 Glycerol polyglycidyl ether (“Denacol” EX313 (manufactured by Nagase ChemteX Corporation)), blocked isocyanate compound (DM-6400 (manufactured by Meisei Chemicals)), rubber latex (pylatex, manufactured by Nippon A&L Co., Ltd.) solid content ratio were mixed at a ratio of 20:40:40 and diluted with water to obtain a precoating agent (P) having a total solid content of 4.0% by weight.
• P precoating agent
• each of the lignin derivative (A), the water-soluble or water-dispersible cross-linking agent (B), and the rubber latex (C) was mixed with water so as to have the ratio shown in Table 1 or Table 2, and the total An adhesive treatment agent having a solid concentration of 15% by weight was obtained.
• the maximum point strength and maximum point elongation of the dry film of the obtained adhesive agent were measured according to the above-described measuring method.
• the rate of change V 30 /V 0 of the liquid viscosity after preparation (V 0 (mPa ⁇ s)) and the liquid viscosity (V 30 (mPa ⁇ s) after 30 days) was determined according to the above-described measurement method for the adhesive agent. was measured.
• Two polyester multifilament yarns of 1670 dtex (“Tetoron” 1670T-360-705M manufactured by Toray Industries, Inc.) were twisted at a base twist of 40 turns/10 cm and a top twist of 40 turns/10 cm to obtain a twisted yarn cord. .
• the twisted yarn cord was immersed in the precoating agent (P), dried at 120°C for 2 minutes, and then heat-treated at 245°C for 1 minute.
• the twisted yarn cord was immersed in an adhesive treatment agent containing the above components (A), (B) and (C), it is dried at 120°C for 2 minutes and then heat-treated at 240°C for 1 minute to obtain a synthetic fiber cord. rice field.
• the treatment with the adhesive treatment agent containing components (A), (B) and (C) was performed by running the cord at a running speed of 20 m/min for 1 hour.
• the amount of coagulum deposited on the turn roll with which the cord is in contact when running in an oven at 120 ° C. is checked, and the coagulum generation state is determined according to the method described in the Examples. evaluated.
• the adhesive solid content adhesion amount of the obtained synthetic fiber cord was 1.1 parts by weight of the precoating agent per 100 parts by weight of the polyester fiber, and the adhesive treatment agent containing (A), (B), and (C) was It was 4.0 parts by weight with respect to 100 parts by weight of the polyester fiber.
• Each component of the adhesive agent shown in Tables 1 and 2 is as follows.
• RF resorcin/formalin molar ratio of 1/1.5
• the mixture was diluted with water to give a 15% solids weight RFL adhesive.
• the amount of the adhesive solid content adhered to the obtained synthetic fiber cord for reinforcing rubber was 1.1 parts by weight for the precoat agent per 100 parts by weight of the polyester fiber, and 4.1 parts by weight for the RFL adhesive per 100 parts by weight of the polyester fiber. It was 0 parts by weight.
• the adhesive treatment agent does not contain resorcin and formalin, which is advantageous in reducing the environmental load compared to the conventional example RFL, and has adhesiveness to rubber and heat-resistant adhesiveness. It can be seen that the fatigue resistance in a high-temperature atmosphere is good. In addition, it can be seen that the storage stability of the adhesive treatment agent is good, and the generation of resin coagulation can be suppressed in the dipping step, and the productivity of synthetic fiber cords for rubber reinforcement is good.

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