JP2016222880A - Latex composition and rfl adhesive containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a PFL adhesive suitable for improving initial adhesive between a rubber and a fiber when a rubber-fiber composite is constituted by using a natural rubber, a styrene butadiene rubber, an ethylene propylene rubber, especially an ethylene propylene rubber and a vulcanizate thereof and adhesiveness after heat deterioration resistance, and a latex composition suitable for the same.SOLUTION: There are provided a latex composition containing at least vinyl chloride polymer particles having an average particle diameter of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle diameter of 1 μm or less and having a content of the vinyl chloride polymer particles to the total amount of the vinyl chloride polymer particles and the chlorosulfonated polyolefin particles of 5 to 20 wt.%, and an RFL adhesive containing the same and a resorcin-formaldehyde condensate dispersion.SELECTED DRAWING: None

Description

  The present invention is a latex composition containing at least vinyl chloride polymer (hereinafter referred to as PVC) particles and chlorosulfonated polyolefin particles, and the latex composition is blended in a resorcin-formaldehyde condensate dispersion. The present invention relates to an RFL (resorcin-formaldehyde condensate-latex) adhesive capable of enhancing the adhesive force between rubber (vulcanized rubber) and fiber, and a latex composition suitable for the adhesive.

  Rubber products are used in the fields of automobile parts such as tires, belts and hoses, industrial parts, and building materials. These products include natural rubber, styrene butadiene rubber, chloroprene rubber and ethylene propylene rubber. A rubber composition containing carbon black, plasticizer, anti-aging agent, vulcanization accelerator, etc. in rubber is blended with fibers such as polyester fiber, nylon fiber and glass fiber impregnated and dried. Many are produced as vulcanized rubber-fiber composites that are vulcanized and bonded.

  As an adhesive for increasing the adhesive force between the vulcanized rubber and the fiber, a condensate solution of resorcin and formaldehyde is added to latex such as vinylpyridine / styrene / butadiene copolymer resin latex (sometimes simply referred to as L liquid). (Hereinafter referred to as RF liquid) mixed resorcinol-formaldehyde condensate-latex adhesive (hereinafter referred to as RFL adhesive), and further RFL adhesive mixed with isocyanate compound, epoxy compound, etc. An adhesive or the like is used. However, when the RFL adhesive is used for adhesion between the ethylene propylene rubber composition and the fiber material, the ethylene propylene rubber has a chemical structure with few double bonds and poor reactivity. There was a problem that the initial adhesive strength and the adhesive strength after heat resistance deterioration could not be sufficiently increased.

  As a method for solving this problem, for example, (1) an adhesive method of a fiber material and rubbers using an adhesive composition of chlorosulfonated polyethylene latex and RF liquid (see, for example, Patent Document 1). ), (2) After treating the fiber material with an RFL adhesive in which an RF liquid is mixed with a rubber latex such as vinylpyridine / styrene / butadiene copolymer resin latex, parachlorophenol and resorcin are added to formaldehyde with RFL adhesive. An adhesion treatment method of polyester fiber and ethylene propylene rubber characterized by treatment with a second treatment liquid to which a co-condensed special chlorophenol compound and a blocked isocyanate compound are added (for example, see Patent Document 2). Proposed.

  An example of an improved adhesive composition for rubber, particularly ethylene-propylene-diene rubber, is an aqueous solution of a half ester of chlorosulfonated polyethylene rubber latex and maleated liquid polybutadiene resin, and in some cases, chlorinated as a second latex. An adhesive composition containing a vinyl polymer latex (see, for example, Patent Document 3) has been proposed.

JP-A-57-105476 (for example, refer to the claims) JP-A-7-216755 (for example, refer to the claims) Japanese Patent Laying-Open No. 2005-519182 (for example, refer to the claims)

  However, in the methods proposed in Patent Documents 1, 2, and 3, the initial adhesive force between the ethylene propylene rubber or ethylene propylene diene rubber and the fiber material and the adhesive force after heat resistance deterioration are certainly excellent. Its adhesive performance is not yet satisfactory.

  The present invention has been made in view of the above problems, and the object thereof is natural rubber, styrene butadiene rubber, rubber such as chloroprene rubber and ethylene propylene rubber, particularly ethylene propylene rubber composition, and vulcanization. The present invention provides a vulcanized rubber-fiber composite having improved initial adhesive strength between rubber and various fibers such as nylon fiber and polyester fiber, and adhesive strength after heat deterioration, and an RFL adhesive and latex composition therefor.

  As a result of intensive studies on the above problems, the inventors of the present invention have found that a latex composition containing a specific proportion of PVC particles having a specific particle size and chlorosulfonated polyolefin particles, and an RFL adhesive comprising the latex composition Was found to be a vulcanized rubber-fiber composite with improved initial adhesive strength and adhesive strength after heat deterioration, and the present invention was completed.

  That is, the present invention is a latex composition comprising at least PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1 μm or less. A latex composition characterized in that the content of PVC particles with respect to the total amount is 5 to 20% by weight, an RFL adhesive comprising the same, a fiber comprising the RFL adhesive and a vulcanized rubber The present invention relates to a vulcanized rubber-fiber composite.

  The present invention is described in detail below.

  The latex composition of the present invention is a latex composition comprising at least PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1 μm or less. The PVC particles and the chlorosulfonated polyolefin particles The content of PVC particles is 5 to 20% by weight with respect to the total amount. Such a latex composition includes, for example, at least a PVC latex containing PVC particles having an average particle diameter of 0.8 μm or less, and a chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle diameter of 1 μm or less. It can be obtained by blending.

  The PVC particles constituting the latex composition of the present invention are PVC particles having an average particle diameter of 0.8 μm or less. Here, when the average particle diameter exceeds 0.8 μm, the vulcanized rubber-fiber composite using the obtained adhesive is inferior in initial adhesive force and adhesive force after heat resistance deterioration. And since the initial adhesive strength of the vulcanized rubber-fiber composite and the adhesive strength after heat deterioration are further improved, the PVC particles have an average particle diameter of 0.07 μm or more and 0.3 μm or less. In particular, PVC particles of 0.07 μm or more and 0.1 μm or less are preferable.

  In addition, the average particle diameter of the PVC particles and the average particle diameter of the chlorosulfonated polyolefin particles in the present invention should be measured, for example, by a particle size distribution measuring device based on the principle of a generally known laser diffraction method and dynamic light scattering method. More specifically, for example, it can be measured by a laser diffraction / scattering particle size measuring device ((trade name) LA-920, Horiba, Ltd.).

  In the present invention, the latex referred to as a latex composition, PVC latex, chlorosulfonated polyolefin latex or the like refers to a dispersion in which fine polymer particles are stably dispersed in a medium represented by an aqueous medium. .

  Examples of the PVC constituting the PVC particles include vinyl chloride homopolymers and vinyl chloride copolymers with vinyl compounds copolymerizable with vinyl chloride. In that case, there is no restriction | limiting in particular as a manufacturing method at the time of manufacturing PVC particle | grains as PVC latex, Any method generally known as a manufacturing method of PVC latex can be used. For example, a vinyl chloride monomer alone or in the presence of a monomer copolymerizable with a vinyl chloride monomer, under gentle stirring with deionized water, an emulsifier (surfactant), and a water-soluble polymerization initiator. Emulsion polymerization method for polymerization, seed emulsion polymerization method for emulsion polymerization using particles obtained by emulsion polymerization method as a seed, monomer of vinyl chloride monomer alone or copolymerizable with vinyl chloride monomer In the presence of deionized water, emulsifier (surfactant), if necessary, emulsification aids such as higher alcohols, oil-soluble polymerization initiators are mixed and dispersed with a homogenizer, etc., and then polymerized with gentle stirring. Examples thereof include a seed micro suspension polymerization method in which polymerization is performed using a seed containing an oil-soluble polymerization initiator obtained by a suspension polymerization method or a micro suspension polymerization method. In particular, a PVC latex obtained by an emulsion polymerization method is preferable because a PVC latex having stable PVC particles can be obtained.

  In the emulsion polymerization, for example, water is used as a dispersion medium, and a polymerization initiator is used in the presence of an emulsifier such as alkylbenzene sulfonate with 5 to 150% by weight of vinyl chloride monomer based on the dispersion medium. The method of superposing | polymerizing under stirring at about 80 degreeC and preferably 40-80 degreeC for 3 to 24 hours can be mentioned.

  Examples of the emulsifier include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate; alkylnaphthalenesulfonates such as sodium alkylnaphthalenesulfonate and potassium alkylnaphthalenesulfonate; alkyldiphenyl ether disulfonic acid. Alkyl diphenyl ether disulfonates such as sodium, potassium alkyl diphenyl ether disulfonate; higher fatty acid salts such as alkali metal laurate, alkali metal myristate, alkali metal palmitate, alkali metal stearate, alkali metal oleate; Alkyl sulfate salts such as sodium lauryl sulfate and sodium myristyl sulfate; polyoxyethylene alkylary Sulfuric acid ester salts: disodium polyoxyethylene alkyl sulfosuccinate, disodium polyoxyethylene alkyl ether sulfosuccinate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene lauryl ether sulfosuccinate, sodium dioctyl sulfosuccinate, sodium dioctyl sulfosuccinate, dihexyl sulfosuccinic acid Examples thereof include sulfosuccinates such as sodium, and these may be used alone or in combination of two or more.

  The PVC latex may contain a chain transfer agent, a reducing agent, a buffering agent and the like.

  The chain transfer agent may be any one that can adjust the degree of polymerization of PVC, such as halogenated hydrocarbons such as trichloroethylene and carbon tetrachloride; 2-mercaptoethanol, octyl 3-mercaptopropionate, dodecyl mercaptan, and the like. Mercaptans; aldehydes such as acetone and n-butyraldehyde.

  Examples of the reducing agent include sodium sulfite, ammonium sulfite, sodium hydrogen sulfite, ammonium hydrogen sulfite, ammonium thiosulfate, potassium metabisulfite, sodium dithionite, L-ascorbic acid, dextrose, ferrous sulfate, Examples thereof include copper sulfate.

  Examples of the buffer include phosphate-hydrogen alkali metal salts, dihydrogen phosphate alkali metal salts, potassium hydrogen phthalate, boric acid-caustic potassium, sodium hydrogen carbonate, and the like.

  Examples of the monomer copolymerizable with the vinyl chloride monomer include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, 1,1-dihydroperfluoroethyl (meth) acrylate, (meth) acryl 1,1-dihydroperfluoropropyl acid, 1,1,5-trihydrperfluorohexyl (meth) acrylate, 1,1,2,2-tetrahydroperfluoropropyl (meth) acrylate, (meth) acrylic acid 1,1 , 7-trihydroperfluoroheptyl, 1,1-dihydroperfluorooctyl (meth) acrylate, (meth 1,1-dihydroperfluorodecyl acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters such as dibutylaminoethyl acid; alkyl vinyl ketone compounds such as methyl vinyl ketone; alkyl vinyl ether compounds such as vinyl ethyl ether; allyl ether compounds such as allyl methyl ether; styrene, α-methyl Styrene, chlorostyrene, vinyltoluene, p-chloromethylstyrene, p-acetoxystyrene, p-acetoxystyrene, p-butoxystyrene, 4-vinylbenzoic acid, 2-vinylpyridine, 4-vinylpyridine, vinylnaphthale Vinyl aromatic compounds such as vinyl; vinyl nitrile compounds such as acrylonitrile and methacrylonitrile; acrylamide; budadiene, 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro- 1,3-butadiene, 2- (N-piperidimethyl) -1,3-butadiene, 2-triethoxymethyl-1,3-butadiene, 2- (N, N-dimethylamino) -1,3-butadiene, N 1,3-butadiene compounds such as-(2-methylene-3-butenoyl) morpholine; others, isoprene, pentadiene, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl propionate, maleic anhydride, citraconic anhydride, Itaconic anhydride, maleic acid, maleic acid ester, fumaric acid ester, crotonic acid, itaconic acid Fumaric acid, methacryloxyxypropyltrimethoxysilane, acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, diacetone methacrylate, vinyl sulfonic acid, 2-acrylamido-1-methyl sulfonic acid, 2-methacrylamide-2- Examples thereof include methyl propane sulfonic acid.

  The production of the PVC latex is completed by reducing the pressure in the container to normal pressure and further reducing the unreacted monomer. In some cases, a polymerization inhibitor may be added to terminate the polymerization. Moreover, an emulsifier etc. can be additionally added to the PVC latex after superposition | polymerization as needed.

  In producing the PVC latex, for the purpose of stabilizing the polymerization and reducing the amount of scale, a reducing agent, a buffer, a thickener, a condensed phosphate, a dispersant, a tackifier, a pH adjuster, Antifoaming agents, preservatives, film-forming aids, anti-aging agents, anti-freezing agents and the like can also be added.

  The chlorosulfonated polyolefin particles are chlorosulfonated polyolefin particles having an average particle diameter of 1 μm or less. Here, when the average particle diameter is more than 1 μm, when the obtained adhesive is applied to the adhesion of the vulcanized rubber-fiber composite, the obtained vulcanized rubber-fiber composite has an initial adhesive force and heat resistance. It will be inferior to the adhesive strength after deterioration. And since it becomes possible to provide a vulcanized rubber-fiber composite with improved initial adhesive strength and adhesive strength after heat deterioration, the average particle size of the chlorosulfonated polyolefin particles is 0.67 μm or more and 0.0. 9 μm or less is preferable.

  The chlorosulfonated polyolefin may be any chlorosulfonated polyolefin as long as it belongs to the category of chlorosulfonated polyolefin, and examples thereof include chlorosulfonated polyethylene and chlorosulfonated polypropylene. In this case, the polyethylene may be an ethylene-α-olefin copolymer, and the polypropylene may be a propylene-α-olefin copolymer. Examples of the α-olefin include 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, and 1-hexene. As a method for producing the chlorosulfonated polyolefin, for example, polyolefins such as polyethylene and polypropylene as raw materials are used, for example, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetra Examples thereof include a solution method in a homogeneous system using a reaction solvent inert to the halogenation reaction such as chloroethane and monochlorobenzene; a suspension method in which polyolefin is suspended in a reaction solvent and reacted. The chlorosulfonated polyolefin after completion of the reaction can be recovered by removing the solvent, and the shape is generally a chip shape, a powder shape or the like.

  When making the chlorosulfonated polyolefin particles into chlorosulfonated polyolefin latex, for example, the chlorosulfonated polyolefin latex can be made by dispersing the chlorosulfonated polyolefin particles in water with an emulsifier or the like.

  The chlorosulfonated polyolefin latex is obtained by converting chlorosulfonated polyolefin into aromatic hydrocarbons such as benzene, toluene and xylene ethylbenzene; chloroform, carbon tetrachloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, It can be produced by dissolving in a solvent such as tetrachloroethane or halogenated hydrocarbon such as monochlorobenzene, carrying out dispersible emulsification in water in the presence of an emulsifier, and then removing the solvent.

  The emulsifier is not particularly limited as long as the chlorosulfonated polyolefin can be emulsified and dispersed in water. Examples thereof include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate; alkylnaphthalenesulfonic acid. Alkylnaphthalene sulfonates such as sodium and potassium alkylnaphthalene sulfonate; Alkyl diphenyl ether disulfonates such as sodium alkyldiphenyl ether disulfonate and potassium alkyldiphenyl ether disulfonate; Alkaline metal laurate, alkali metal myristate, and alkali metal palmitate Salts, higher fatty acid salts such as alkali metal stearate and alkali metal oleate; sodium lauryl sulfate, myristyl Alkyl sulfate salts such as sodium acid ester; polyoxyethylene alkylaryl sulfate salts; disodium polyoxyethylene alkylsulfosuccinate, disodium polyoxyethylene alkyl ether sulfosuccinate, sodium dialkylsulfosuccinate, polyoxyethylene lauryl ether sulfosuccinic acid Examples thereof include sulfosuccinates such as sodium, sodium dioctylsulfosuccinate, sodium dioctylsulfosuccinate, sodium dihexylsulfosuccinate, and the like. These may be used alone or in combination of two or more.

  The chlorosulfonated polyolefin latex can be made more stable by containing a basic substance. Examples of the basic substance at that time include sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, diethanolamine, morpholine and the like.

  Examples of the emulsifying device for forming a latex include a homomixer, a homogenizer, a homomic line mixer emulsifying device, etc., and conditions such as a stirring speed and a stirring time so that the chlorosulfonated polyolefin is sufficiently dispersed in water. It is possible to make latex by adjusting.

  Moreover, what is necessary is just to heat and remove by reducing pressure as a method of removing a solvent from an emulsified liquid when making it into latex. At this time, it is also possible to adjust the latex concentration by simultaneously removing water as necessary.

  The chlorosulfonated polyolefin latex includes a vulcanizing agent, a vulcanization accelerator, an acid acceptor, a reinforcing agent, a filler, a descending aid, a softening agent, a plasticizer, an antiaging agent, a resin, a film forming aid, and a wetting agent. Properties improvers, pigments, dyes, thixotropic agents, viscosity modifiers, antifoaming agents, antifungal agents and the like may be added as necessary.

  The latex composition of the present invention has a PVC particle content of 5 to 20% by weight based on the total amount of PVC particles and chlorosulfonated polyolefin particles. Here, when the content of PVC particles is less than 5% by weight, when the obtained composition is an RFL adhesive and applied to a vulcanized rubber-fiber composite, the resulting vulcanized rubber-fiber composite is In addition, the initial adhesive strength and the adhesive strength after heat resistance deterioration are inferior. On the other hand, also when the content of PVC particles exceeds 20% by weight, the initial adhesive strength and the adhesive strength after heat deterioration of the vulcanized rubber-fiber composite are similarly deteriorated.

  The latex composition of the present invention is obtained by blending with a resorcin-formaldehyde condensate dispersion (hereinafter referred to as RF solution) to produce a vulcanized rubber-fiber composite having excellent initial adhesive strength and adhesive strength after heat deterioration. It can be an RFL (resorcin-formaldehyde condensate-latex) adhesive that can be provided. Any method may be used as a method for producing the RFL adhesive at that time, for example, a method of blending the latex composition containing the PVC particles and the chlorosulfonated polyolefin particles with an RF solution, and other RF solutions. A method of blending the chlorosulfonated polyolefin particles (latex) and the PVC particles (latex) into the same.

  The RF liquid is a dispersion of a condensate of resorcin and formaldehyde, such as bishydroxyalkylphenol such as 1,3-benzenediol, 1,5-benzenediol, bishydroxymethylphenol, and bishydroxyethylphenol. This is an aqueous solution of a condensate of resorcin and formaldehyde, and can be produced using a basic catalyst such as sodium hydroxide, potassium hydroxide and ammonia, or an acid catalyst such as hydrochloric acid and sulfuric acid. .

  The RFL adhesive of the present invention comprises the latex composition and the RF liquid, and may contain an isocyanate compound, a blocked isocyanate compound, an epoxy compound, or the like as necessary.

  Examples of the isocyanate compound include polyisocyanates such as tolylene diisocyanate, m-phenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and polymethylene polyphenyl polyisocyanate; compounds having these isocyanates and two or more active hydrogen atoms, for example, And polyhydric alcohol-added polyisocyanate compounds which are reaction products with trimethylolpropane, pentaerythritol and the like.

  Examples of the blocked isocyanate compound include polyisocyanates such as aromatic secondary amines such as diphenylamine and xylidine; phthalic imides; lactams such as caprolactam and valerolactam; acetoxime, methyl ethyl ketone oxime, cyclohexane oxime and the like. Examples thereof include blocked polyisocyanate compounds obtained by reacting a blocking agent such as oximes.

  The epoxy compound is not particularly limited, but a polyepoxide compound having two or more epoxy groups in the molecule, for example, polyhydric alcohols such as ethylene glycol, glycerol, sorbitol, pentaerythritol, and polyethylene glycol Reaction product with halogen-containing epoxides such as epichlorohydrin; Reaction product of polyphenols such as resorcin, bis (4-hydroxyphenyl) dimethylmethane, phenol / formaldehyde resin and the halogen-containing epoxides; 3,4-epoxy Examples include cyclohexene epoxide, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6-methyl-cyclomethyl) adipate, and the like.

  In addition, the isocyanate compound, the blocked isocyanate compound, and the epoxy compound can be used as a fiber treating agent in the vulcanized rubber-fiber composite. In this case, the fibers were directly treated with these. The treatment with the RFL adhesive of the present invention may be performed later.

  The RFL adhesive containing the latex composition of the present invention is effective for the treatment of the fibers constituting the vulcanized rubber-fiber composite, and the treated fibers have improved adhesion to the vulcanized rubber. It is. Examples of the fiber at that time include polyester fiber, nylon fiber, aramid (aromatic polyamide) fiber, glass fiber, carbon fiber, rayon fiber, vinylon fiber, and soot, but are not particularly limited. The shape of the fiber includes various forms such as a thread, a cord, a woven fabric, a nonwoven fabric, a sheet, a short fiber, a film, and a sheet, but is not particularly limited.

  The method of treating the fiber with the RFL adhesive of the present invention is not particularly limited. For example, 1) a method of impregnating and drying the fiber with an immersion liquid of the RFL adhesive of the present invention, 2) an isocyanate compound, and a blocked isocyanate compound Alternatively, the epoxy compound is previously diluted in an organic solvent such as water or ethyl acetate, immersed in a fiber and dried, and then impregnated and dried with the RFL adhesive of the present invention. 3) Isocyanate compound, blocked isocyanate compound Or the method of impregnating and drying a fiber in the immersion liquid of the RFL adhesive of the present invention containing an epoxy compound can be used.

  As the fiber impregnation treatment with the RFL adhesive of the present invention, in order to promote resinification of the RFL adhesive and chemical bonding with the fiber, after performing a drying treatment to remove moisture at 80 to 150 ° C., 150 ° C. or higher It is preferable to perform heat treatment (baking) at a temperature of.

  The vulcanized rubber-fiber composite of the present invention is composited by vulcanizing a blend of a rubber composition and fibers, and the rubber composition at that time is also called raw rubber. It is a rubber compound obtained by mixing raw rubber and auxiliary raw materials composed of a filler, a plasticizer, a vulcanizing agent, a vulcanization accelerator, an antiaging agent, a processing aid and the like.

  The raw material rubber is not particularly limited. For example, natural rubber (NR), styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber, halogenated butyl rubber and the like are unsaturated. Type rubbers; saturated type rubbers such as chlorosulfonated polyethylene (CSM), chlorinated polyethylene, hydrogenated nitrile rubber, ethylene propylene rubber, epichlorohydrin rubber, fluororubber, acrylic rubber, and silicone rubber; More than one species may be used in combination. Among them, the RFL adhesive of the present invention particularly efficiently acts on ethylene propylene rubber.

  Examples of auxiliary materials include fillers such as carbon black, mica, silica, clay, magnesium hydroxide, aluminum hydroxide, graphite, mica, and ferrite; paraffinic oil, naphthenic oil, aroma oil, soybean oil, Vegetable oil such as rapeseed oil, phthalates such as dibutyl phthalate and dioctyl phthalate, plasticizers such as liquid rubber such as liquid butadiene rubber; vulcanizing agents such as sulfur and benzoyl peroxide; tetramethylthiuram disulfide and tetraethyl Vulcanization accelerators such as thiuram disulfide, morpholinodithiobenzothiazole, diphenylthiourea, diphenylguanidine, mercaptobenzothiazole, N-sulfenamide, zinc dimethyldicarbamate, magnesium oxide, red lead; phthalic anhydride, nito Anti-scorching agents such as sodiphenylamine; anti-aging agents such as N-isopropyl N′-phenyl-p-phenylenediamine, 2,6-di-t-butylcatechol, mercaptobenzimidazole; raw materials such as thioxylenol and dixyl disulfide Kneading accelerators; Active agents such as wax and stearic acid; Tackifiers such as terpene phenol, gum rosin and tall oil rosin; Foaming agents such as sodium bicarbonate, azodicarbonamide, p, p'-oxybis (benzenesulfonylhydrazide) Etc.

  When the raw rubber and the auxiliary raw material are mixed to obtain a rubber composition, a method of mixing and dispersing using a mixer such as an open roll, a pressure kneader, or a Banbury mixer can be employed.

  And when the fiber which processed with the RFL adhesive agent containing the latex composition of this invention is a cord, a textile fabric, a sheet | seat etc., this fiber and this rubber composition are closely_contact | adhered and vulcanize | cured this, for example Thus, a vulcanized rubber-fiber composite having excellent adhesion between the vulcanized rubber and the fiber can be obtained. In addition, when the fiber subjected to the treatment with the RFL adhesive containing the latex composition of the present invention is a short fiber, for example, the rubber composition and the short fiber are kneaded and vulcanized to vulcanize. A vulcanized rubber-fiber composite having excellent adhesion between the vulcanized rubber and the fiber can be obtained. Examples of the vulcanization method include press vulcanization, steam vulcanization, hot air vulcanization, UHF vulcanization, electron beam vulcanization, molten salt vulcanization, and the like, and any method may be used.

  By molding the vulcanized rubber-fiber composite of the present invention, a vulcanized rubber-fiber composite molded body can be obtained. Examples of the molding method include calendering, extrusion molding, injection molding, and compression molding.

  By forming the vulcanized rubber-fiber composite of the present invention into a molded body, rubber hoses for automobiles, industrial hoses, air springs for trucks and buses, V belts, toothed belt conveyor belts, power transmission belts, etc. It can be used for a wide variety of applications such as various types of belts such as automobile belts and industrial belts, tires such as automobile tires and motorcycle tires, civil engineering and construction sheets, and daily goods for rubber footwear.

  The latex composition of the present invention and the RFL adhesive containing the latex composition can provide a fiber excellent in adhesion to (vulcanized) rubber, and can be provided with a vulcanized rubber-fiber composite, particularly an ethylene propylene rubber composite. In this case, the initial force between fibers and the adhesive strength after heat deterioration are also excellent.

  The present invention will be specifically described by the following examples and comparative examples.

  In addition, the evaluation methods of PVC latex containing PVC particles, chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles, latex composition, RFL adhesive, and vulcanized rubber-fiber composite in the following Examples and Comparative Examples are as follows. It is as follows.

<Average particle size>
The average particle size of PVC latex containing PVC particles and chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles was measured by adding water so that the laser transmittance was 84 to 86%, respectively. The sample was measured for particle size distribution using a laser diffraction / scattering particle size measuring device (trade name: LA-920, manufactured by HORIBA, Ltd.) to determine the median diameter, and the average particle size was obtained.

<Measurement of initial adhesive strength of vulcanized rubber-fiber composite>
A sheet of the rubber composition-fiber composite that was left in a temperature-controlled room (25 ° C., relative humidity 65%) for 1 day or longer was made into a strip-shaped test piece having a width of 25 mm and a length of 100 mm or more in accordance with JISK6502. The test piece used the tensile tester (Orientec company make, type RTM-500), calculated | required peeling force by the peeling test between a rubber composition and a fiber at the peeling rate of 50 mm / min, and was taken as the initial adhesive force.

<Measurement of adhesive strength after heat resistance deterioration of vulcanized rubber-fiber composite>
The rubber composition-fiber composite sheet was post-cured at 175 ° C. for 6 hours in a gear oven, the vulcanized rubber-fiber composite sheet was peeled in the same manner as the initial adhesive strength, and was heat-resistant. It was set as the later adhesive force.

Production Example 1 (PVC latex 1)
In a 2.5 L polymerization can, 800 g of deionized water, 600 g of vinyl chloride monomer, 9.6 g of 5 wt% potassium laurate aqueous solution and 0.16 g of potassium persulfate were charged, and the temperature was raised to 56 ° C. to initiate polymerization. From 150 minutes after the start of the polymerization, 45 g of a 5 wt% aqueous potassium laurate solution and 125 g of a 5 wt% aqueous sodium dodecylbenzenesulfonate solution were added at a rate of 17 ml per hour, and the addition was stopped after 480 minutes. When the pressure in the polymerization can is reduced to 0.5 MPa, unreacted vinyl chloride monomer is recovered to obtain PVC latex 1 having an average particle diameter of 0.26 μm and a concentration of PVC particles of 32.6% by weight. It was.

Production Example 2 (PVC latex 2)
As initial charge in a 2.5 L autoclave, 900.0 g of deionized water, 750.0 g of vinyl chloride monomer, 5.0 g of 3 wt% potassium persulfate aqueous solution and 5 wt% sodium dodecylbenzenesulfonate aqueous solution 75 The emulsion polymerization was started by charging 0.0 g and raising the temperature to 66 ° C. The temperature was kept at 66 ° C., and the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, and then the unreacted vinyl chloride monomer was recovered. To this, 235.0 g of a 5% by weight aqueous sodium dodecylbenzenesulfonate solution was added to obtain PVC latex 2 having an average particle size of 0.10 μm and a concentration of PVC particles of 37.0% by weight.

Production Example 3 (PVC latex 3)
Except that the potassium laurate aqueous solution was not charged at the time of charging, the same operation as in Production Example 1 was performed to obtain PVC latex 3 having an average particle diameter of 0.56 μm and a PVC concentration of 32.6% by weight.

Production Example 4 (PVC latex 4)
A 1 m ³ autoclave was charged with 500 kg of deionized water, 300 kg of vinyl chloride monomer, 200 g of bis (1-methylheptyl) peroxydicarbonate, 12 kg of a 25 wt% aqueous sodium lauryl sulfate solution, and 4.5 kg of lauryl alcohol. The mixture was circulated using a homogenizer for minutes, and after the homogenization treatment, the temperature was raised to 48 ° C. to proceed the polymerization. When the polymerization pressure dropped from the saturated vapor pressure of vinyl chloride monomer at 48 ° C. by 2 kg / cm ² , the polymerization reaction was stopped, unreacted vinyl chloride monomer was recovered, the average particle size was 0.95 μm, and the PVC concentration 32.6% by weight of PVC latex 4 was obtained.

Production Example 5 (Chlorosulfonated polyolefin latex 1)
30 g of chlorosulfonated polyethylene ((trade name) TS-320, manufactured by Tosoh Corporation) and 270 g of toluene as a chlorothrophonated polyolefin were added to a 0.5 L stirrer and a four-necked flask equipped with a condenser and heated to 90 ° C The mixture was stirred for 3 hours to obtain a 10% by weight chlorosulfonated polyethylene-toluene solution. The obtained toluene solution was 6.9 g of a 10% by weight potassium hydroxide solution, a 25.3% aqueous solution 3 of polyoxyethylene (3) sodium lauryl lauryl ether sulfate ((trade name) EMAL 20C, manufactured by Kao Corporation). .6 g was put into a container containing an aqueous solution dissolved in 337.5 g of water and forced emulsification was performed at 10,000 rpm for 10 minutes using a homogenizer on a 60 ° C. hot water bath to obtain an emulsion of a chlorosulfonated polyethylene-toluene solution. It was. The obtained emulsion was evaporated using an evaporator under reduced pressure at 60 ° C., and toluene and water were distilled off. After filtration through a 200-mesh filter cloth, the average particle size was 0.81 μm, and the concentration of chlorosulfonated polyethylene particles was 30.5. A weight percent chlorosulfonated polyolefin latex 1 was obtained.

Production Example 6 (Chlorosulfonated polyolefin latex 2)
The average particle size was 0.67 μm and the concentration of chlorosulfonated polyethylene particles was 31 in the same manner as in Production Example 5, except that the 25.3% aqueous solution of polyoxyethylene (3) sodium lauryl lauryl ether sulfate was changed to 3.7 g. 0.0% by weight of chlorosulfonated polyolefin latex 2 was obtained.

Production Example 7 (Chlorosulfonated polyolefin latex 3)
The average particle size was 0.92 μm and the concentration of chlorosulfonated polyethylene particles was 31. 3 in the same manner as in Production Example 5 except that 3.0 g of a 25.3% aqueous solution of sodium polyoxyethylene (3) lauryl lauryl ether sulfate was used. 6% by weight of chlorosulfonated polyolefin latex 3 was obtained.

Production Example 8 (Chlorosulfonated polyolefin latex 4)
The average particle size was 1.22 μm and the concentration of chlorosulfonated polyethylene particles was 30. The same procedure as in Production Example 5 except that 2.4 g of a 25.3% aqueous solution of polyoxyethylene (3) sodium lauryl lauryl ether sulfate was used. 0% by weight of chlorosulfonated polyolefin latex 4 was obtained.

Example 1
In a container equipped with a 0.5 liter stirrer, 24.1 g of PVC latex 1 composed of PVC particles having an average particle diameter of 0.26 μm obtained in Production Example 1 and an average particle diameter of 0.2 mm obtained in Production Example 5 were obtained. 232.1 g of chlorosulfonated polyolefin latex 1 composed of 81 μm chlorosulfonated polyethylene particles were added and stirred, and PVC particles with an average particle size of 0.26 μm were (PVC particles + chlorosulfonated polyolefin particles) as a whole. Thus, 256.3 g of a latex composition containing 10% by weight and having a solid content of 30.7% by weight was obtained.

  On the other hand, 11.0 g of resorcin, 16.2 g of 37% formaldehyde aqueous solution (formalin), 0.7 g of sodium hydroxide and 232 g of water as a catalyst were added to a container equipped with a 0.5 liter stirrer, and stirred at room temperature for 5 hours. As a result, 260 g of a resorcin-formaldehyde condensate dispersion (RF solution) having a resin solid content of 6.8% was obtained.

  Then, add 256.3 g of the latex composition and 260 g of the RF solution to a 1 liter container, and after stirring at room temperature for 20 hours, add 2.1 g of a water-soluble epoxy compound ((trade name) SR4GL, manufactured by Sakamoto Yakuhin). An RFL adhesive having a solid concentration of 18.7% by weight was prepared by stirring for 10 minutes.

  Nylon cloth (Shikishima Canvas Co., Ltd., (trade name) N-856) cut into 16 cm × 16 cm as a fiber is immersed in 500 g of RFL adhesive for 10 minutes, dried in a gear oven at 140 ° C., and treated with RFL adhesive treated fiber. did.

  The rubber composition was prepared by kneading A and B kneading an ethylene propylene rubber composition 13 times as much as the following composition using ethylene propylene rubber as a raw rubber. The A kneading was prepared using a 3 liter pressure kneader, and the B kneading using a 12 inch roll.

(A training)
Ethylene propylene rubber ((trade name) EP21, manufactured by JSR Corporation) 100.0 parts by weight Zinc white 5.0 parts by weight Stearic acid 1.0 part by weight FEF carbon black 50.0 parts by weight Process oil ((trade name) SUNPAR150 , Made by Nippon Sun Oil Co., Ltd.) 10.0 parts by weight (B kneaded)
Sulfur 1.0 part by weight Zinc dibutyldithiocarbamate 1.0 part by weight Tetramethylthiuram disulfide 1.0 part by weight 2-mercaptobenzothiazole 1.0 part by weight Then, nylon fabric treated with RFL adhesive treatment liquid A rubber composition-fiber composite was prepared by scissoring with a rubber composition to obtain a rubber composition-fiber composite and press vulcanizing at 160 ° C. for 30 minutes. Thereafter, it was left in a thermostatic chamber (25 ° C., relative humidity 65%) for 1 day or longer, and the initial adhesive strength was measured. Moreover, the adhesive force after heat-resistant deterioration measured the adhesive force after putting a vulcanized rubber-fiber composite in 175 degreeC oven and carrying out the heat deterioration for 6 hours. The results are shown in Table 1.

  As is apparent from Table 1, obtained using an RFL adhesive obtained from a latex composition comprising PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less. The obtained vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) had excellent initial adhesive strength and adhesive strength after heat deterioration.

Examples 2-3
PVC latexes 2 and 3 containing PVC particles having an average particle diameter of 0.8 μm or less obtained in Production Examples 2 to 3 and chlorosulfonated polyolefin particles having an average particle diameter of 1.0 μm or less obtained in Production Examples 6 to 7 A latex composition, an RFL adhesive, a treated fiber, a rubber composition-fiber composite (ethylene propylene rubber composition-) in the same manner as in Example 1 except that the chlorosulfonated polyolefin latex 2 and 3 were used. Nylon fiber composite) and vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 1.

  As is apparent from Table 1, using an RFL adhesive obtained from a latex composition comprising PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less. The obtained vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) had excellent initial adhesive strength and adhesive strength after heat deterioration.

Example 4
As shown in Table 1, the average particle size was 0 in the same manner as in Example 1 except that the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) was 5% by weight. A latex composition comprising PVC latex 1 containing PVC particles of .26 μm and chlorosulfonated polyolefin latex 1 containing chlorosulfonated polyolefin particles having an average particle diameter of 0.81 μm, RFL adhesive, treated fiber, rubber composition A fiber composite (ethylene propylene rubber composition-nylon fiber composite) and a vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 1.

  As is apparent from Table 1, using an RFL adhesive obtained from a latex composition comprising PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less. The obtained vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) had excellent initial adhesive strength and adhesive strength after heat deterioration.

Example 5
As shown in Table 1, the average particle size was 0 in the same manner as in Example 1 except that the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) with respect to the entire particles was 20% by weight. PVC latex 1 containing PVC particles of .8 μm or less, and chlorosulfonated polyolefin latex 1 containing chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less, RFL adhesive, treated fiber, rubber composition-fiber composite (Ethylene propylene rubber composition-nylon fiber composite) and vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 2.

  As is apparent from Table 2, using an RFL adhesive obtained from a latex composition comprising PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less. The obtained vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber composition-nylon fiber composite) had excellent initial adhesive strength and adhesive strength after heat deterioration.

Example 6
Tetron cloth (Shikishima) that was dissolved in 998 g of water by stirring 2 g of water-soluble epoxy compound ((trade name) SR4GL, manufactured by Sakamoto Yakuhin Co., Ltd.) for 10 minutes in a 0.2 liter container, transferred to another container, and cut into 16 cm x 16 cm (Product name: T-81, manufactured by Canvas Inc.) was immersed for 10 minutes, dried in a gear oven at 140 ° C. for 10 minutes, and used in the same manner as in Example 1 except that a tetron fiber previously treated with epoxy was used. Latex composition containing PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less by the method, RFL adhesive, treated fiber, rubber composition-fiber composite (ethylene propylene-based) Rubber composition-nylon fiber composite) and vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 2.

  As is apparent from Table 2, using an RFL adhesive obtained from a latex composition comprising PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less. The obtained vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) had excellent initial adhesive strength and adhesive strength after heat deterioration.

Examples 7-8
Using the pre-epoxy-treated tetron fiber obtained in Example 6, PVC latexes 2 and 3 containing PVC particles having an average particle diameter of 0.56 μm and 0.10 μm in Examples 2 to 3, and an average particle diameter of 0. Latex composition containing chlorosulfonated polyolefin latex 2, 3 containing chlorosulfonated polyolefin particles of 81 μm and 0.67 μm, RFL adhesive, treated fiber, rubber composition-fiber composite (ethylene propylene-based rubber composition- Tetron fiber composites) and vulcanized rubber-fiber composites were prepared and evaluated. The results are shown in Table 2.

  As is apparent from Table 2, using an RFL adhesive obtained from a latex composition comprising PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less. The obtained vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) had excellent initial adhesive strength and adhesive strength after heat deterioration.

Example 9
Using the epoxy-treated tetron fiber obtained in Example 6, PVC latex 1 containing PVC particles having an average particle diameter of 0.26 μm of Example 6 and chlorosulfonated polyolefin particles having an average particle diameter of 0.81 μm are included. A latex composition comprising a chlorosulfonated polyolefin latex 1 and containing 5% by weight of PVC particles (PVC particles + chlorosulfonated polyolefin particles) with respect to the entire particle, RFL adhesive, treated fiber, rubber composition A product-fiber composite (ethylene propylene rubber composition-tetron fiber composite) and a vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 2.

  As is apparent from Table 2, using an RFL adhesive obtained from a latex composition comprising PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less. The obtained vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-tetron fiber composite) had excellent initial adhesive strength and adhesive strength after heat resistance deterioration.

Example 10
Using the epoxy-treated tetron fiber obtained in Example 6, PVC latex 1 containing PVC particles having an average particle diameter of 0.26 μm of Example 6 and chlorosulfonated polyolefin particles having an average particle diameter of 0.81 μm are included. A latex composition comprising 20% by weight of PVC particles (PVC particles + chlorosulfonated polyolefin particles) composed of chlorosulfonated polyolefin latex 1 with respect to the total particles, RFL adhesive, treated fiber, rubber composition A product-fiber composite (ethylene propylene rubber composition-tetron fiber composite) and a vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 2.

  As is apparent from Table 2, an RFL adhesive obtained from a latex composition containing PVC particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1.0 μm or less is used. The initial adhesive strength and the adhesive strength after heat resistance deterioration of the vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-tetron fiber composite) thus obtained were excellent.

Comparative Example 1
In the same manner as in Example 1, PVC latex 4 containing PVC particles with an average particle size of 0.95 μm obtained in Production Example 4 and chlorosulfonation with an average particle size of 1.22 μm obtained in Production Example 8 Composition comprising chlorosulfonated polyolefin latex 4 containing polyolefin particles, adhesive, treated fiber, rubber composition-fiber composite (ethylene propylene rubber composition-nylon fiber composite), vulcanized rubber-fiber composite Prepared and evaluated. The results are shown in Table 3.

  As is apparent from Table 3, a composition containing a PVC latex containing PVC particles having an average particle diameter exceeding 0.8 μm and a chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle diameter exceeding 1.0 μm. The vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) obtained by using the adhesive obtained from the product was inferior in initial adhesive strength and adhesive strength after heat deterioration.

Comparative Example 2
In the same operation as in Example 1, except that the PVC particles 4 having an average particle diameter of 0.95 μm obtained in Production Example 4 were used, the same operation as in Example 1 was carried out. A rubber composition-fiber composite (ethylene propylene rubber composition-nylon fiber composite) and a vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 3.

  As is apparent from Table 3, a vulcanized rubber-fiber composite (vulcanized) obtained using an adhesive obtained from a composition containing PVC latex containing PVC particles having an average particle diameter of more than 0.8 μm. The initial adhesive strength of the ethylene propylene rubber-nylon fiber composite) and the adhesive strength after heat resistance deterioration were inferior.

Comparative Example 3
In the same operation as in Example 1, except that the chlorosulfonated polyolefin latex 8 having an average particle size of 1.22 μm obtained in Production Example 8 was used, the same procedure as in Example 1 was followed. Treated fiber, rubber composition-fiber composite (ethylene propylene rubber composition-nylon fiber composite), and vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 3.

  As is apparent from Table 3, a vulcanized rubber obtained by using an adhesive obtained from a composition containing a chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle diameter exceeding 1.0 μm The initial adhesive strength of the fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) and the adhesive strength after heat resistance deterioration were inferior.

Comparative Example 4
As shown in Table 3, the average particle size was 0 in the same manner as in Example 1 except that the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) was 2% by weight. Composition, adhesive, treated fiber, rubber composition-fiber composite comprising PVC latex containing .26 μm PVC particles and chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle size of 0.81 μm Ethylene propylene rubber composition-nylon fiber composite) and vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 3.

  As is apparent from Table 3, an adhesive obtained from a composition containing a composition in which the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) is as small as 2% by weight with respect to the whole particles is used. The initial adhesive strength of the vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) obtained as described above and the adhesive strength after heat deterioration were inferior.

Comparative Example 5
As shown in Table 3, the average particle size was 0 in the same manner as in Example 1 except that the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) relative to the entire particles was 30% by weight. A composition, an adhesive, a treated fiber, a rubber composition-fiber composite comprising a PVC latex containing .26 μm PVC particles and a chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle diameter of 0.81 μm ( Ethylene propylene rubber composition-nylon fiber composite) and vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 3.

  As is apparent from Table 3, an adhesive obtained from a composition containing a composition having a large content of 30% by weight of PVC particles (PVC particles + chlorosulfonated polyolefin particles) with respect to the whole particles is used. The initial adhesive strength of the vulcanized rubber-fiber composite (vulcanized ethylene propylene rubber-nylon fiber composite) obtained as described above and the adhesive strength after heat deterioration were inferior.

Comparative Example 6
PVC latex 4 containing PVC particles having an average particle size of 0.95 μm in Production Example 4 and chlorosulfonated polyolefin particles having an average particle size of 1.22 μm in Production Example 8 using the pre-epoxy-treated tetron fiber of Example 6 A composition comprising a chlorosulfonated polyolefin latex 4 containing, an adhesive, a treated fiber, a rubber composition-fiber composite (ethylene propylene rubber composition-tetron fiber composite), and a vulcanized rubber-fiber composite were prepared. The evaluation was performed. The results are shown in Table 4.

  As is apparent from Table 4, an adhesive obtained from a composition comprising a PVC latex containing PVC particles with an average particle size greater than 0.8 μm and a chlorosulfonated polyolefin latex containing PVC particles greater than 1.0 μm was used. The initial adhesive strength of the vulcanized rubber-fiber composite (vulcanized ethylene propylene-based rubber-tetron fiber composite) obtained as described above and the adhesive strength after heat deterioration were inferior.

Comparative Example 7
The same procedure as in Example 1 except that the PVC latex 4 having an average particle size of 0.95 μm obtained in Production Example 4 was used in the same manner as in Example 1, using the pre-epoxy-treated tetron fiber of Example 6. By the above operations, a composition, an adhesive, treated fibers, a rubber composition-fiber composite (ethylene propylene rubber composition-tetron fiber composite), and a vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 4.

  As is apparent from Table 4, a vulcanized rubber-fiber composite (vulcanized ethylene) obtained by using an adhesive obtained from a composition containing a latex containing PVC particles having an average particle diameter exceeding 0.8 μm. The initial adhesive strength of the propylene rubber-tetron fiber composite) and the adhesive strength after heat resistance deterioration were inferior.

Comparative Example 8
Except for using the pre-epoxy-treated tetron fiber of Example 6 and using the chlorosulfonated polyolefin latex 8 having an average particle diameter of 1.22 μm obtained in Production Example 8 in the same manner as in Example 1, Example In the same manner as in No. 1, a composition, adhesive, treated fiber, rubber composition-fiber composite (ethylene propylene rubber composition-tetron fiber composite), and vulcanized rubber-fiber composite were prepared and evaluated. went. The results are shown in Table 4.

  As is apparent from Table 4, a vulcanized rubber obtained using an adhesive obtained from a composition containing a chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle diameter of more than 1.0 μm The initial adhesive strength and the adhesive strength after heat deterioration of the fiber composite (vulcanized ethylene propylene rubber-tetron fiber composite) were inferior.

Comparative Example 9
Similar to Example 13, except that the pre-epoxy-treated Tetron fiber of Example 6 was used and the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) was 2% by weight based on the entire particle. Composition comprising a PVC latex containing PVC particles having an average particle size of 0.26 μm and a chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle size of 0.81 μm A composition-fiber composite (ethylene propylene rubber composition-tetron fiber composite) and a vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 4.

  As is apparent from Table 4, an adhesive obtained from a composition containing a composition in which the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) is as small as 2% by weight with respect to the whole particles is used. The vulcanized rubber-fiber composite (vulcanized ethylene propylene-based rubber-tetron fiber composite) obtained in this manner was inferior in initial adhesive strength and adhesive strength after heat deterioration.

Comparative Example 10
Similar to Example 13, except that the pre-epoxy-treated Tetron fiber of Example 6 was used and the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) was 30% by weight with respect to the whole particles. Composition comprising a PVC latex containing PVC particles having an average particle size of 0.26 μm and a chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle size of 0.81 μm A composition-fiber composite (ethylene propylene rubber composition-tetron fiber composite) and a vulcanized rubber-fiber composite were prepared and evaluated. The results are shown in Table 4.

  As is apparent from Table 4, an adhesive obtained from a composition containing a composition in which the content of PVC particles (PVC particles + chlorosulfonated polyolefin particles) is as large as 30% by weight with respect to the whole particles is used. The vulcanized rubber-fiber composite (vulcanized ethylene propylene-based rubber-tetron fiber composite) obtained in this manner was inferior in initial adhesive strength and adhesive strength after heat deterioration.

  By using the latex composition of the present invention and the RFL adhesive containing the latex composition, it is excellent in initial adhesive strength between rubber, particularly ethylene propylene rubber and fiber, and adhesive strength after heat deterioration. The vulcanized rubber-fiber composite has high industrial applicability such as automotive rubber hoses, industrial hoses, air springs for trucks and buses, V belts, toothed belt conveyor belts, and the like.

Claims (6)

A latex composition comprising at least vinyl chloride polymer particles having an average particle size of 0.8 μm or less and chlorosulfonated polyolefin particles having an average particle size of 1 μm or less, wherein the vinyl chloride polymer particles and the chlorosulfonated polyolefin particles A latex composition, wherein the content of vinyl chloride polymer particles is 5 to 20% by weight relative to the total amount. It is formed by blending at least a vinyl chloride polymer latex containing vinyl chloride polymer particles having an average particle diameter of 0.8 μm or less and a chlorosulfonated polyolefin latex containing chlorosulfonated polyolefin particles having an average particle diameter of 1 μm or less. The latex composition according to claim 1. An RFL adhesive comprising the latex composition according to claim 1 or 2 and a resorcin-formaldehyde condensate dispersion. A vulcanized rubber-fiber composite comprising a fiber impregnated with the RFL adhesive according to claim 3 and a vulcanized rubber.   The vulcanized rubber-fiber composite according to claim 4, wherein the vulcanized rubber is a vulcanized ethylene propylene rubber. A vulcanized rubber-fiber composite molded article obtained by molding the vulcanized rubber-fiber composite according to claim 4 or 5.