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
  • 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
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J193/00—Adhesives based on natural resins; Adhesives based on 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
  • D06M13/395—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
• • 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
  • D06M15/17—Natural resins, resinous alcohols, resinous acids, 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
  • D06M15/39—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
  • D06M15/693—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 treatment agent for synthetic fibers capable of improving the adhesiveness between rubber and synthetic fibers, a synthetic fiber cord that can be suitably used for rubber reinforcement, and a rubber product reinforced by the synthetic fiber cord. ..
• Synthetic fibers such as nylon fibers, polyester fibers, and aromatic polyamide fibers have been widely used as reinforcing materials in rubber products such as tires, hoses, and belts.
• synthetic fibers such as nylon fibers, polyester fibers, and aromatic polyamide fibers
• rubber products such as tires, hoses, and belts.
• it is used as a reinforcing material by being embedded in a rubber product, it is exposed to high temperatures due to the heat generated by the rubber, and due to repeated stretching, compression and bending, the adhesiveness between the rubber and the synthetic fiber is increased. The decrease and the decrease in the strength of synthetic fibers occurred, which was a factor leading to the failure of rubber products.
• Patent Documents 1 to 4 As the technology disclosed for the above problem, for example, the prior art of Patent Documents 1 to 4 is known.
• Patent Document 1 discloses a code having an impregnation degree of 3.5 to 9% for a resorcin formalin latex (hereinafter, may be abbreviated as "RFL”) adhesive.
• RTL resorcin formalin latex
• Patent Document 2 is coated with a first treatment agent containing three kinds of an aliphatic epoxide compound, a blocked polyisocyanate compound, and a vinylpyridine, styrene, and butadiene rubber latex having a glass transition point of ⁇ 30 to 0 ° C.
• the outer layer is a polyester fiber cord for rubber reinforcement coated with a second treatment agent containing RFL, and the first bath hot stretch tension is treated with 0.05 to 0.40 cN / dtex.
• a method for manufacturing a polyester fiber cord for rubber reinforcement, which is a feature thereof, is disclosed.
• Patent Document 3 an organic having a lower twist and an upper twist, and a various twist cord having a lower twist twist coefficient of 1000 to 2500 and an upper twist twist coefficient of 1500 to 3600 coated with an adhesive containing RFL.
• a fiber cord is disclosed, wherein the cord has a compressibility of 83 to 97% and an RFL impregnation into the cord has a degree of impregnation of 10 to 50%.
• Patent Document 4 describes at least one component selected from the group consisting of polyphenols, chlorphenol resin and lignin resin, and at least one selected from a water-soluble polymer other than the above component or a water-dispersible polymer other than the above component.
• an adhesive for organic fibers containing one component Disclosed is an adhesive for organic fibers containing one component.
• Patent Document 1 the fatigue resistance is improved, but the adhesive strength is not sufficient.
• Patent Documents 2 and 3 the adhesive strength and fatigue resistance are also improved as compared with the conventional ones, but the durability is not sufficient as the required level increases.
• Patent Document 4 the initial adhesive strength is improved, but the heat-resistant adhesive strength and durability are not sufficient.
• the present invention has been made as a result of studying the solution of the above-mentioned problems in the prior art as a problem.
• An object of the present invention is that there is little deterioration in adhesive strength under high temperature for a long time when embedded in rubber such as a tire, belt, or hose, and deterioration when repeatedly stretched and compressed in rubber is suppressed. It is an object of the present invention to provide a treatment agent for a fiber suitable for reinforcing a rubber which can be used, and an object of the present invention is to provide a synthetic fiber cord having an excellent rubber reinforcing effect.
• the present invention employs the following means in order to solve such a problem. That is, (1) A treatment agent containing at least lignin (A) and a blocked isocyanate compound (B), and the maximum strength of the dry film when the treatment agent is a dry film is 0.2 MPa to 1. A treatment agent characterized by being 6 MPa. (2) The treatment agent according to (1) above, wherein the maximum point elongation of the dry film is 2% to 120%. (3) The above (1) or (2), wherein the weight ratio ((A): (B)) of the lignin (A) to the blocked isocyanate compound (B) is 10: 1 to 10:30. The treatment agent according to any one of.
• the treatment agent described in Crab. contains the rubber latex (C), and the weight ratio of the rubber latex (C) to the weight of the lignin (A) and the blocked isocyanate compound (B) contained in the treatment agent (((A)). ) + (B)): (C)) according to any one of (1) to (4) above, wherein the adhesive treatment agent for rubber / fiber is 10: 90 to 60:40.
• a synthetic fiber cord having significantly improved adhesiveness and fatigue resistance in a high temperature atmosphere when exposed to high temperatures for a long period of time, such as during a rubber vulcanization process or use as a rubber product can be obtained.
• the rubber product reinforced with the synthetic fiber cord according to the present invention can withstand harsh specifications for a longer time than before when used as a tire, belt, or hose.
• the treatment agent of the present invention can improve the adhesiveness to rubber when the synthetic fiber is treated, and can suppress the deterioration of the adhesiveness between the fiber and rubber even in a high temperature environment.
• the treatment agent of the present invention contains at least lignin (A) and a blocked isocyanate compound (B), and the maximum point strength of the dry film when the adhesive treatment agent is a dry film is 0.2 MPa to 1.6 MPa. It is necessary to be.
• Lignin (A) used in the present invention is an aromatic polymer present in trees and is known as a natural polymer compound having a phenylpropane skeleton as a basic structure.
• the lignin (A) used in the present invention includes a state in which lignin is chemically treated as well as a state in which it is naturally produced.
• Such examples include, for example, kraft lignin obtained from kraft pulp waste liquid, lignin sulfonic acid obtained from sulfite pulp waste liquid, and the like in the paper manufacturing process using wood as a raw material.
• the lignin sulfonic acid has a sulfonic group introduced into the side chain of the phenylpropane structure of lignin, and may be in the form of a salt, for example, sodium lignin sulfonate, magnesium lignin sulfonate, calcium lignin sulfonate, etc. Can be mentioned. In the present invention, these can be used alone or in combination, but sodium lignin sulfonate can be most preferably used from the viewpoint of adhesive strength.
• the blocked isocyanate compound (B) used in the present invention is a compound capable of producing an active isocyanate compound by liberating the blocking agent by heating, and specifically, tolylene diisocyanate, metaphenylenedi isocyanate, diphenylmethane diisocyanate, and hexa.
• Blocks of polyisocyanate compounds such as methylindiisocyanate and triphenylmethane triisocyanate and phenols such as phenol, cresol and resorcin, lactams such as ⁇ -caprolactam and valerolactam, and oximes such as acetoxime, methylethylketooxime and cyclohexaneoxime. Examples include reaction products with agents.
• diphenylmethane diisocyanate is preferably used because an aromatic polyisocyanate compound blocked with ⁇ -caprolactam or methylethylketooxime gives a high reinforcing effect.
• the treatment agent of the present invention contains at least lignin (A) and a blocked isocyanate compound (B), and the maximum point strength of the dry film when the adhesive treatment agent is a dry film is 0.2 MPa to 1.6 MPa. It is necessary to be, preferably 0.3 MPa to 1.4 MPa. If it is less than 0.2 MPa, the adhesive strength may be insufficient, and if it exceeds 1.6 MPa, the fatigue resistance may be deteriorated.
• the method for preparing the dry film and the method for measuring the maximum point strength are the methods described in the section of Examples. However, if it is difficult to use this method, an equivalent method can be used.
• the lignin (A) and the blocked isocyanate compound (B) are contained in the same treatment agent, and the maximum point strength of the dry film of the adhesive treatment agent is within the above-specified range. It is essential to have. Adhesion that is contained in the same treatment agent and is within the specified range of the present invention to exhibit excellent adhesion between rubber and fiber and excellent fatigue resistance of fiber in rubber in a high temperature atmosphere. It becomes a treatment agent.
• the treatment agent of the present invention preferably has a maximum point elongation of 2% to 120%, more preferably 4% to 100%, when the treatment agent is used as a dry film. .. If it is less than 2%, the fatigue resistance may be deteriorated, and if it exceeds 120%, the adhesiveness may be insufficient.
• the method for preparing the dry film and the method for measuring the maximum point elongation are the methods described in the section of Examples. 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 treatment agent can be adjusted by the type of drug contained in the treatment agent and the mixing ratio.
• the maximum point strength can be adjusted to be high by increasing the content of the blocked isocyanate compound (B) contained in the treatment agent.
• the maximum point elongation can be adjusted to be high by mixing the rubber latex with the treatment agent and increasing the mixing amount.
• the content of lignin (A) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. It is% by weight. If it is less than 5% by weight or more than 50% by weight, the adhesive strength may be insufficient.
• the weight ratio ((A) :( B)) of the lignin (A) to the blocked isocyanate compound (B) is preferably 10: 1 to 10:30, more preferably 10: 5 to 10:20. Is. If the amount of blocked isocyanate compound is small in the range exceeding this weight ratio, the adhesive strength may be insufficient, and if the amount of blocked isocyanate compound is large in the range exceeding this weight ratio, the cord becomes hard and fatigue resistance. May get worse.
• the treatment agent of the present invention preferably further contains a rubber latex (C).
• the (C) rubber latex that can be used in the present invention include natural rubber latex, butadiene rubber latex, styrene / butadiene / rubber latex, vinylpyridine / styrene / butadiene rubber latex, nitrile rubber latex, hydride nitrile rubber latex, and chloroprene.
• examples thereof include rubber latex, chlorosulfonated rubber latex, ethylene / propylene / diene rubber latex, and these can be used alone or in combination.
• the lignin (A), the blocked isocyanate compound (B) and the rubber latex (C) are the weights of the lignin (A) and the blocked isocyanate compound (B) and the rubber latex (C). It is preferable that the weight ratio (((A) + (B)): (C)) is contained in the ratio of 10:90 to 60:40. More preferably, the weight ratio (((A) + (B)) :( C)) is 20:80 to 50:50. If it is out of this range, the adhesive strength may be insufficient or the fatigue resistance may be deteriorated.
• the treatment 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 7 to 20% by weight. If it is out of this range, it may not be possible to impart a sufficient amount of solid content to the fiber, or cohesive failure may occur at the treatment agent solid content, which may lead to a decrease in adhesive strength. ..
• the synthetic fiber cord of the present invention can be suitably used for reinforcing rubber, but the synthetic fiber is treated with the above-mentioned treatment agent.
• the treatment agent preferably contains a rubber latex (C), and preferred embodiments of lignin, blocked isocyanate and rubber latex are as described above in the description of the treatment agent of the present invention.
• treated means the state of the treatment agent after the treatment agent is applied to the synthetic fiber and then dried or heat-treated.
• volatile components contained in the treatment agent for example, a solvent such as water are distilled off, and the protecting group of the blocked isocyanate is removed to cause a reaction with the isocyanate group. That is, the synthetic fiber treated with the treatment agent is in a state of being attached to or bonded to the synthetic fiber without the solid content of the treatment agent being chemically modified or modified.
• the amount of the treatment agent applied to the synthetic fiber it is preferable to give an amount such that the solid content weight of the treatment agent is 1 part by weight to 15 parts by weight with respect to 100 parts by weight of the synthetic fiber, and more preferably.
• the solid content weight of the agent is preferably 1.5 parts by weight to 10 parts by weight. If it goes out of this range, the adhesive strength may decrease.
• the synthetic fiber used in the synthetic fiber cord of the present invention is preferably in the form of a multifilament.
• the material constituting the synthetic fiber include nylon 6, nylon 66, nylon 46, polyethylene terephthalate, polyethylene naphthalate, aramid, polyvinyl alcohol, and the like. From the viewpoint of durability and industrial productivity, it is preferable to contain at least one selected from nylon fiber, polyester fiber and aromatic polyamide fiber. Further, at least one fiber selected from nylon fiber, polyester fiber, and aromatic polyamide fiber has 60% by weight or more, preferably 80% by weight or more, more preferably 90% by weight, when the total weight of the synthetic fiber is 100% by weight. It is preferable to occupy the above.
• the polyester fiber is preferably a fiber obtained by melt-spinning and drawing a polyester containing terephthalic acid as the main bifunctional carboxylic acid and ethylene glycol as the main glycol component, but partly or all of the terephthalic acid is 2,6-. Fibers made of polyester in which naphthalenedicarboxylic acid, 4,4-dicarboxyphenoxyetane, isocyanate group, etc. are replaced, or polyester in which ethylene glycol is partially or wholly replaced with diethylene glycol, propylene glycol, butanediol, etc. are also used. be able to.
• the polyester may be a copolymer of a trifunctional compound such as trimesic acid, trimellitic acid, boric acid, phosphoric acid, glycerin, and trimethylolpropane in a small amount.
• a trifunctional compound such as trimesic acid, trimellitic acid, boric acid, phosphoric acid, glycerin, and trimethylolpropane in a small amount.
• polyester fiber may be modified with various modifiers, for example, a terminal carboxyl group blocking agent such as a carbodiimide compound, an epoxy compound, an isocyanate compound, and an oxazoline compound.
• a terminal carboxyl group blocking agent such as a carbodiimide compound, an epoxy compound, an isocyanate compound, and an oxazoline compound.
• the aromatic polyamide fiber is made of poly-p-phenylene terephthalamide, poly-p-phenylene terephthalamide, 3,4'-diphenyl ether terephthalamide copolymer, or a copolymer mainly composed of these. Is preferably used.
• the synthetic fiber used in the present invention may be previously added with a polyepoxide compound in the silk reeling process.
• the polyepoxide compound include compounds containing at least two or more epoxy groups in one molecule in an amount of 0.1 g or more per 100 g of the compound. Specifically, it is unsaturated with a reaction product of polyhydric alcohols such as pentaerythritol, ethylene glycol, polyethylene glycol, propylene glycol, glycerol and sorbitol with halogen-containing epoxides such as epichlorohydrin, peroxidation or hydrogen peroxide.
• polyhydric alcohols such as pentaerythritol, ethylene glycol, polyethylene glycol, propylene glycol, glycerol and sorbitol
• halogen-containing epoxides such as epichlorohydrin, peroxidation or hydrogen peroxide.
• Polyepoxide compounds obtained by oxidizing compounds such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6-methyl-cyclohexylmethyl) adipate, phenol novolac type
• aromatic polyepoxides such as hydroquinone type, biphenyl type, bisphenol S type, brominated novolak type, xylene-modified novolak type, phenol glioxal type, trisoxyphenylmethane type, trisphenol PA type, and bisphenol type polyepoxides.
• Particularly preferred are sorbitol glycidyl ether type and cresol novolak type polyepoxides.
• polyepoxide compounds are usually used as emulsions or solutions. That is, the above compound is dissolved in a solvent and used as a solution, or emulsified with a usual emulsifier such as sodium alkylbenzene sulfonic acid, sodium dioctylsulfosuccinate salt, nonylphenolethylene oxide adduct and the like, and used as an emulsifying solution.
• a usual emulsifier such as sodium alkylbenzene sulfonic acid, sodium dioctylsulfosuccinate salt, nonylphenolethylene oxide adduct and the like, and used as an emulsifying solution.
• the polyepoxide compound is applied together with a spinning oil agent in the process of producing synthetic fibers.
• the adhered amount of the polyepoxide compound at this time is preferably in the range of 0.1 to 5% by weight.
• the amount of the polyepoxide compound adhered is within the above range, the effect of the polyepoxide compound is sufficiently exhibited, and a satisfactory adhesiveness between the synthetic fiber and the rubber can be obtained. Further, within the above range, the fibers do not become too hard, and the strength is unlikely to decrease in the plying process described later.
• the synthetic fiber used in the present invention is not restricted by the fineness, the number of filaments, the cross-sectional shape, etc., but usually 200 to 5000 dtex, 30 to 1000 filament circular cross-sectional yarn is used, and 250 to 3000 dtex, 50 to 500 filaments are used. Circular cross-section yarn is preferred.
• the synthetic fiber cord of the present invention is obtained by twisting the synthetic fiber into a twisted cord, and the twisted cord is woven as it is or in a streak shape and then dipped with the adhesive treatment agent of the present invention. It can be obtained by heat treatment.
• a twisted cord used for a carcass tire cord is twisted in the S direction or the Z direction, and then two or three lower twist cords are combined and usually the same number of upper twists are applied in the opposite direction to the lower twist.
• a twisted cord can be used.
• the twisted cord is used as a warp, a cotton thread is covered with a weft, or a cotton thread is covered with an organic fiber to form a weft, and the bamboo blind is woven into a bamboo blind to form a bamboo blind.
• Heat treatment is performed to obtain a dip fabric.
• a lower twist is applied, and two or three of them are combined and usually the same number of upper twists are applied in the direction opposite to the lower twist to form a twisted cord of various twists.
• it is dipped with an adhesive and heat treated to make a dip cord.
• the synthetic fiber cord treated with the treatment agent of the present invention includes both the case of the above dip roll and the case of the dip cord.
• the synthetic fiber cord of the present invention is dipped and heat-treated with a primer treatment agent containing an epoxy compound before the twisted yarn cord is dip-treated and heat-treated with a treatment agent containing at least lignin (A) and a blocked isocyanate compound (B).
• the primer treatment agent may be applied to the synthetic fiber.
• the synthetic fiber cord of the present invention is a treatment agent containing resorcin formalin latex (RFL) after dipping and heat-treating the twisted yarn cord with a treatment agent containing at least lignin (A) and a blocked isocyanate compound (B). It may be treated with, for example, a treatment agent containing isocyanate formalin latex (RFL) is dipped and then heat-treated.
• RTL resorcin formalin latex
• Resorcin formalin latex is a mixture consisting of resorcin formaldehyde initial condensate and rubber latex.
• the resorcin formalin latex is particularly preferably prepared using a resorcin formaldehyde initial condensate obtained by initial condensation under an alkaline catalyst. For example, resorcin and formaldehyde are added and mixed in an alkaline aqueous solution containing an alkaline compound such as sodium hydroxide, allowed to stand at room temperature for several hours, initial condensation of resorcin and formaldehyde, and then a rubber latex is added to the mixed emulsion. It is prepared by the method of.
• the resorcin / formaldehyde initial condensate preferably has a molar ratio of resorcin to formaldehyde of 1: 0.3 to 1: 5, preferably 1: 0.75 to 1: 2.0. If the molar ratio of formaldehyde is less than the above range, the dip cord becomes sticky and may cause stains on the dip processing machine, while if the molar ratio of formaldehyde is higher than this range, the adhesive strength is reduced. Sometimes.
• Examples of the rubber latex used for preparing resorcin formalin latex include natural rubber latex, butadiene rubber latex, styrene / butadiene rubber latex, vinylpyridine / styrene / butadiene rubber latex, nitrile rubber latex, hydride nitrile rubber latex, and chloroprene.
• Examples thereof include rubber latex, chlorosulfonated rubber latex, ethylene / propylene / diene rubber latex, and these can be used alone or in combination.
• the compounding ratio of resorcin / formaldehyde initial condensate and rubber latex should be 2/1 to 1/12 as [resorcin / formaldehyde initial condensate weight / rubber latex weight] by solid content weight. Is preferable. If it goes out of this range, the adhesive strength may decrease.
• the solid content concentration of the treatment agent containing RFL is preferably 3 to 20% by weight.
• the amount of the treatment agent containing RFL attached to the synthetic fiber is such that the solid content weight of the treatment agent with respect to 100 parts by weight of the synthetic fiber is in the range of 0.5 to 10 parts by weight from the viewpoint of adhesiveness and fatigue resistance. preferable. If it exceeds 10 parts by weight, it may cause stains on the dip processing machine described later.
• the synthetic fiber cord for rubber reinforcement of the present invention characterized by the above has remarkable fatigue resistance during the rubber vulcanization process and the use of rubber products. It will be improved.
• the rubber product reinforced with the synthetic fiber cord for rubber reinforcement according to the present invention is extremely useful for rubber reinforcement because it can withstand harsh use for a longer period of time than before when used as a tire, belt and hose. ..
• the twisted cord of the synthetic fiber is dipped in the treatment agent of the present invention, and subsequently, the moisture is dried at a temperature of preferably 100 to 150 ° C., and then 200 to 255. This is a method of applying heat treatment at ° C.
• the dip means that the plying cord is applied to the twisted cord by running the plying cord in a dip tank in which a roller is installed inside and the treatment agent is filled.
• the heat treatment refers to heating the plying cord by running the plying cord in an oven in which a roller is installed and the temperature can be set to a predetermined temperature.
• a dip processing machine that performs such a dip and heat treatment, for example, it is commercially available from Ritzler.
• any method for adhering the treatment agent to the synthetic fiber any method such as spraying the treatment agent from a nozzle and applying the treatment agent to the synthetic fiber can be adopted.
• means such as squeezing with a pressure welding roller, scraping with a scraper, blowing off with air blowing, and suction may be used.
• the synthetic fiber cord can be slidably contacted with the edge to perform a softening treatment for obtaining arbitrary cord rigidity.
• the same dipping method as the above method can be adopted. That is, the synthetic fiber cord obtained above is dipped in an adhesive treatment agent containing RFL, and the moisture is preferably dried at a temperature of 100 to 150 ° C., followed by heat treatment at 200 to 255 ° C. The same method as described above can be adopted for controlling the amount of solid content attached and for the softening treatment.
• the synthetic fiber cord of the present invention thus obtained has significantly improved heat-resistant adhesiveness and fatigue resistance when exposed to high temperatures for a long time during the rubber vulcanization process or the use of rubber products.
• the rubber product reinforced with the synthetic fiber cord according to the present invention is extremely useful for rubber reinforcement because it can withstand harsh use for a longer period of time than before when used as a tire, belt and hose.
• Adhesion amount of treatment agent was determined according to the mass method of the dip pickup of JIS L-1017 (2002).
• T-Initial Adhesive Strength and T-Heat-Resistant Adhesive Strength The adhesive strength between the synthetic fiber cord and rubber is shown.
• the initial adhesive strength is measured by embedding a synthetic fiber cord in unvulcanized rubber and pressing vulcanizing at 150 ° C. for 30 minutes in accordance with the 3.1T test (method A) of Annex 1 of JIS L-1017 (2002). After cooling, the synthetic fiber cord was pulled out from the rubber block at a speed of 300 mm / min, the weight required for the pulling out was obtained for each sample, and the arithmetic average value of 10 samples was used as the T-. The initial adhesive strength was used.
• the heat-resistant adhesive strength is measured by embedding the synthetic fiber cord in unvulcanized rubber and pressing at 170 ° C for 70 minutes in accordance with the 3.1T test (method A) of Annex 1 of JIS L-1017 (2002). After vulcanization, it is allowed to cool, and after cooling, the synthetic fiber cord is pulled out from the rubber block at a rate of 300 mm / min, the weight required for the pulling out is obtained for each sample, and the arithmetic average value of 10 samples is used as T. -Heat-resistant adhesive strength.
• the composition of the unvulcanized rubber compound used for measuring the T-initial adhesive strength, the T-heat resistant adhesive strength, and the fatigue resistance in rubber is as follows.
• Zinc oxide 5 (part by weight) 2,2'-Dithiobenzothiazole: 3 (part by weight) Naphthenic acid process oil: 3 (part by weight).
• the strength and elongation at the point where the intensity becomes the maximum value are obtained for each sample, the arithmetic average value of the intensity at the number of samples 6 is used as the maximum point strength, and the calculated average value of the elongation at the number of samples 6 is used as the maximum point elongation. And said.
• Example 1 As lignin (A), 12 g of sodium lignin sulfonate (manufactured by Nippon Paper Industries, Ltd., Sun Extract P252) was dissolved in 459 g of water, and here, as blocked isocyanate (B), Elastron BN27 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was dissolved. , 40 g of solid content concentration 30%. Compound in which diphenylmethane diisocyanate is blocked by a blocking agent) is further mixed, and as rubber latex (C), Nipponol 2518FS (manufactured by Nippon Zeon Co., Ltd., solid content concentration 40.5%).
• B blocked isocyanate
• Elastron BN27 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
• a treatment agent containing 89 g of a treatment agent having a total solid content concentration of 10% by weight (a treatment agent containing lignin (A) and blocked isocyanate (B) (to avoid misunderstanding, a case where a rubber latex (C) is contained) is included. (Additional note) is referred to as a “lignin treatment agent” for convenience. Hereinafter, the same applies to other Examples and Comparative Examples).
• the maximum point strength and maximum point elongation of the obtained dry film of the adhesive treatment agent were measured. The results are shown in Table 1.
• the molar ratio of resorcin / formalin was mixed at a ratio of 1 / 1.4 in the presence of caustic soda, adjusted to a solid content concentration of 10%, and aged for 2 hours to perform the initial stage of resorcin and formalin.
• a condensate was obtained.
• the mixture was diluted with water to give an RFL adhesive with a solid content of 15%.
• Two 1670 dtex polyester multifilament yarns (“Tetron” 1670T-360-705M manufactured by Toray Industries, Inc.) were twisted with a twist number of 40 times / 10 cm for bottom twist and 40 times / 10 cm for top twist to obtain a twisted yarn cord. ..
• the plying cord was immersed in the lignin treatment agent using a calculator processing machine (manufactured by Ritzler Co., Ltd.), dried at 120 ° C. for 2 minutes, and then heat-treated at 245 ° C. for 1 minute. Subsequently, after immersing in the RFL adhesive treatment agent, it was dried at 120 ° C. for 2 minutes, and then heat-treated at 245 ° C. for 1 minute to obtain a synthetic fiber cord.
• a calculator processing machine manufactured by Ritzler Co., Ltd.
• the amount of the adhesive solid content adhered to the obtained synthetic fiber cord was 4 parts by weight with respect to 100 parts by weight of the synthetic fiber for those derived from the lignin treatment agent, and 4 parts by weight with respect to 100 parts by weight of the adhesive containing RFL. It was 3 parts by weight.
• the synthetic fiber cord thus obtained was embedded in unvulcanized rubber and vulcanized, and then T-initial adhesive strength, T-heat-resistant adhesive strength, and fatigue resistance in rubber were measured. The results are shown in Table 1.
• Example 2 6 g of sodium lignin sulfonate (manufactured by Nippon Paper Co., Ltd., "Sun Extract” P252) as lignin (A) was dissolved in 468 g of water, and DM3031 (manufactured by Meisei Chemical Works, Ltd.) was used as a blocked isocyanate (B). A solid content concentration of 54% and 22 g of ⁇ -caprolactum-blocked diphenylmethane diisocyanate were mixed, and 104 g of Nipponol 2518FS (manufactured by Nippon Zeon Co., Ltd., solid content concentration of 40.5%) was further mixed as a rubber latex (C). A lignin treatment agent having a total solid content concentration of 10% by weight was obtained. Subsequent processing was the same as in Example 1. Table 1 shows various measurement results of the obtained synthetic fiber cord.
• Example 3 The same treatment as in Example 1 was carried out except that the lignin (A) was changed to magnesium lignin sulfonate (manufactured by Nippon Paper Industries, Ltd., “Sun Extract” P321). Table 1 shows various measurement results of the obtained synthetic fiber cord.
• Example 4 21 g of sodium lignin sulfonate (manufactured by Nippon Paper Industries, Ltd., "Sun Extract” P252) as lignin (A) was dissolved in 465 g of water, and here, as blocked isocyanate (B), "Elastron” BN27 (Daiichi Kogyo Seiyaku Pharmaceutical Co., Ltd.) 70 g of Nippon Zeon Co., Ltd. (solid content concentration 30%) is mixed, and 44 g of Nippon Zeon Co., Ltd. (solid content concentration 40.5%) is further mixed as rubber latex (C) to make a total solid. A lignin treatment agent having a concentration of 10% by weight was obtained. Subsequent processing was the same as in Example 1. Table 1 shows various measurement results of the obtained synthetic fiber cord.
• Example 5 36 g of sodium lignin sulfonate (manufactured by Nippon Paper Industries, Ltd., "Sun Extract” P252) as lignin (A) was dissolved in 489 g of water, and here, as blocked isocyanate (B), "Elastron” BN27 (Daiichi Kogyo Seiyaku Pharmaceutical Co., Ltd.) 60 g of Nippon Zeon Co., Ltd. (solid content concentration 30%) is mixed, and 15 g of Nippon Zeon Co., Ltd. (solid content concentration 40.5%) is further mixed as rubber latex (C) to make a total solid. A lignin treatment agent having a concentration of 10% by weight was obtained. Subsequent processing was the same as in Example 1. Table 1 shows various measurement results of the obtained synthetic fiber cord.
• Example 6 2.4 g of sodium lignin sulfonate (manufactured by Nippon Paper Co., Ltd., "Sun Extract” P252) as lignin (A) was dissolved in 453 g of water, and here, as the blocked isocyanate of the component (B), "Elastron” BN27 ( 8 g of Daiichi Kogyo Seiyaku Co., Ltd. (solid content concentration 30%) is mixed, and 136 g of Nipponol 2518FS (Nippon Zeon Co., Ltd., solid content concentration 40.5%) is further mixed as the rubber latex of the component (C). The mixture was mixed to obtain an adhesive treatment agent having a total solid content concentration of 10% by weight. Subsequent processing was the same as in Example 1. Table 1 shows various measurement results of the obtained synthetic fiber cord.
• Example 7 The same treatment as in Example 1 was carried out except that the treatment with the RFL adhesive treatment agent was not carried out in Example 1. Table 1 shows various measurement results of the obtained synthetic fiber cord.

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• 2021
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