JP6040751B2 - Adhesive aid, RFL adhesive treatment liquid and rubber composition-fiber composite - Google Patents

Description

  The present invention relates to an adhesion aid, an RFL adhesive treatment solution, and a rubber composition-fiber composite, and in particular, an initial adhesion force between a rubber composition and a fiber, an adhesion force after heat deterioration, and a heat bending resistance after fatigue. The present invention relates to an adhesion aid for enhancing adhesive strength, an RFL adhesive treatment liquid containing the adhesion aid, and a rubber composition-fiber composite obtained by treatment with the RFL adhesive treatment liquid.

  Rubber products such as tires, belts, hoses and air springs are used in fields such as automobile parts, industrial parts and building materials. These products are made from rubber such as natural rubber, styrene butadiene rubber, and chlorosulfonated polyethylene, and rubber compositions containing carbon black, plasticizer, anti-aging agent, vulcanization accelerator, etc. are impregnated with adhesive. -Manufactured as a composite of vulcanized and bonded fibers such as dried polyester fiber, polyamide fiber, and glass fiber.

  Examples of the adhesive that enhances the adhesion between the rubber composition and the fibers include resorcin-formalin condensate solution (RF liquid), and processing liquid in which a rubber latex such as vinylpyridine styrene butadiene copolymer resin latex is mixed with the RF liquid. (RFL liquid), and further, a treatment liquid in which an isocyanate compound, an epoxy compound, or the like is mixed with the RFL liquid is used. These adhesives increase the adhesion between rubber and fiber, but by using a halogen-based rubber latex or a specific proportion of vinylpyridine-conjugated diene-based rubber latex to increase the adhesion after heat-resistant fatigue bending. Various fiber and rubber bonding methods have been proposed.

  (1) a glass fiber treated with a treatment liquid containing vinylpyridine-styrene-butadiene terpolymer latex, butadiene latex and RF liquid, and then treated with a treatment liquid containing chlorosulfonated polyethylene, isocyanate, a vulcanizing agent and a lead compound; Rubber composites have been proposed to increase the strength of rubber products such as rubber belts and tires (for example, Patent Document 1). This method surely provides an adhesive composition for organic fiber cords that can maintain good adhesion after rubber vulcanization, but has problems in adhesion and bending fatigue after vulcanization for a long time. Moreover, since lead is used, there is an environmental problem, and there is a problem that the fiber used is limited to glass fiber.

  (2) The polyester fiber is heat-treated at 90 ° C. or higher, then dipped in a treatment liquid in which an RF solution and a vinylpyridine-conjugated diene copolymer latex are mixed, and further a specific proportion of vinylpyridine-conjugated diene rubber latex. There has been proposed a method for bonding a tetron fiber treated with a rubber and a rubber (for example, Patent Document 2). Although this method certainly provides an adhesive composition for organic fiber cords that can maintain good adhesion after rubber vulcanization, it can be used for adhesion after prolonged vulcanization and during high-speed running when used in automobile tires. There was a problem in lowering the adhesive strength due to fatigue deterioration of the reinforcing fibers. Moreover, the fiber used also had the subject limited to a tetron fiber.

JP-A 63-126975 JP-A-1-96224

  The present invention has been made in view of the above problems, and its purpose is to provide an initial adhesive force between various fibers such as tetron fiber, nylon fiber, and glass fiber and various rubber compositions such as natural rubber and styrene butadiene rubber. , Adhesive aid excellent in heat-resistant adhesive strength between heat-degraded fiber and rubber composition, heat-resistant bending fatigue, RFL adhesive treatment solution containing the adhesion aid, and treatment with the RFL adhesive treatment solution Another object of the present invention is to provide a rubber composition-fiber composite obtained.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific vinyl chloride resin latex can solve the above-mentioned problems, and have completed the present invention. That is, the present invention includes a soap-free chloride containing a copolymer containing vinyl chloride and 0.2 to 6% by weight of an epoxy group-containing vinyl, containing no surfactant and having an average particle size of 1.0 μm or less. An adhesion aid containing a vinyl resin latex, an RFL adhesive treatment liquid containing an aqueous solution of resorcin and formalin condensate and an RFL liquid containing rubber latex, and a rubber composition obtained by treatment with the RFL adhesive treatment liquid An object-fiber composite.

  Hereinafter, the present invention will be described in detail.

  The adhesion assistant of the present invention contains a specific soap-free vinyl chloride resin latex.

  The soap-free vinyl chloride resin latex contained in the adhesion aid of the present invention contains a copolymer containing vinyl chloride and 0.2 to 6% by weight of an epoxy group-containing vinyl, does not contain a surfactant, and The average particle size is 1.0 μm or less.

  The soap-free vinyl chloride resin latex contains a copolymer containing vinyl chloride and 0.2 to 6% by weight of an epoxy group-containing vinyl. The content of the epoxy group-containing vinyl in the copolymer is 0.2 to 6% by weight. When it is less than 0.2% by weight, the initial adhesive strength, the adhesive strength after heat resistance deterioration, and the adhesive strength after heat resistance bending fatigue are inferior. When it exceeds 6% by weight, the initial adhesive strength is excellent, but the adhesive strength after heat-resistant deterioration and the adhesive strength after heat-resistant bending fatigue are inferior.

  Examples of the epoxy group-containing vinyl include glycidyl esters of (meth) acrylic acid such as glycidyl methacrylate (glycidyl methacrylate), glycidyl acrylate (glycidyl acrylate), β-methyl glycidyl methacrylate, β-methyl glycidyl acrylate, maleic acid, Examples thereof include diglycidyl esters and allyl glycidyl ethers of vinyl polymerizable unsaturated carboxylic acids such as fumaric acid and itaconic acid, and two or more of these may be contained.

  The soap-free vinyl chloride resin latex does not contain a surfactant. When the surfactant is included, the initial adhesive strength of the rubber composition-fiber composite between the rubber composition and the fiber treated with the RFL solution containing the adhesion aid, the adhesive strength after heat deterioration, and after heat bending fatigue Adhesive strength is impaired.

  The term “surfactant” as used herein refers to a substance that exhibits remarkable surface activity (action that dissolves in water and lowers the surface tension of water) in a small amount, such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, Examples of anionic surfactants include alkyl sulfates such as sodium lauryl sulfate and myristyl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate. , Sulfosuccinates such as sodium dioctylsulfosuccinate, fatty acid salts such as ammonium laurate and potassium stearate, polyoxyethylene alkyl sulfates, polyoxyethylene alkylaryl sulfates, etc. Examples of the surfactant include sorbitan esters such as sorbitan monooleate and polyoxyethylene sorbitan monostearate, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyalkylene glycol, polyvinyl alcohol, and partial saponification. Examples of the cationic surfactant include stearyl amiacetate and lauryltrimethylammonium chloride. Examples of the amphoteric surfactant include lauryldimethylamine oxide and laurylcarboxymethylhydroxy. Examples include ethyl imidazolium betaine.

  The soap-free vinyl chloride resin latex can contain a carboxylic acid vinyl ester in addition to vinyl chloride and an epoxy group-containing vinyl. By including the carboxylic acid vinyl ester, the polymer can have a hydroxyl group by the saponification reaction of the carboxylic acid vinyl ester, the initial adhesive strength of the rubber composition-fiber composite, the adhesive strength after heat deterioration, The adhesive strength after heat-resistant bending fatigue is further improved. Examples of the carboxylic acid vinyl ester include vinyl acetate, vinyl propionate, vinyl myristate, vinyl benzoate and the like, and two or more of these can be used.

  The soap-free vinyl chloride resin latex has an average particle size of 1.0 μm or less. When the average particle diameter exceeds 1.0 μm, the initial adhesive force of the rubber composition-fiber composite of the rubber composition and the fiber treated with the RFL liquid containing the adhesion aid, the adhesive force after heat deterioration, and the heat bending Adhesive strength after fatigue is impaired. In order to further improve the adhesive force of the rubber composition-fiber composite, the average particle size is preferably 0.3 to 0.8 μm.

  The soap-free vinyl chloride resin latex can be produced by emulsion polymerization. Emulsion polymerization uses water or a mixed solvent of water and an organic solvent that can be mixed with water (for example, methanol, ethanol, acetone, etc.) as a dispersion medium, and a vinyl chloride monomer and 0.2 to 6% by weight of epoxy. A group-containing vinyl monomer, or a vinyl chloride monomer, 0.2 to 6% by weight of an epoxy group-containing vinyl monomer and a carboxylic acid vinyl ester monomer in an aqueous medium not containing a surfactant The polymerization initiator is used, and is obtained by dissolving the chain transfer agent in the monomer as necessary at 30 to 100 ° C., preferably 3 to 24 hours at 60 to 90 ° C., and carrying out the polymerization with stirring. . The soap-free vinyl chloride resin latex can be used by blending two or more soap-free vinyl chloride resin latexes.

  Examples of the epoxy group-containing vinyl monomer include glycidyl esters of (meth) acrylic acid such as glycidyl methacrylate (glycidyl methacrylate), glycidyl acrylate (glycidyl acrylate), β-methyl glycidyl methacrylate, and β-methyl glycidyl acrylate, Examples thereof include diglycidyl esters of vinyl polymerizable unsaturated carboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and two or more of these may be used.

  Examples of the carboxylic acid vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl myristate, vinyl benzoate and the like, and two or more of these can be used.

  In the emulsion polymerization, a monomer copolymerizable with a vinyl chloride monomer can be used as necessary. Examples of the monomer copolymerizable with the vinyl chloride monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid or anhydrides thereof, methyl acrylate, ethyl, butyl and the like. Esters, methyl methacrylate ethyl, ethyl, butyl and the like: unsaturated carboxylic acid esters such as maleic acid ester, fumaric acid ester and cinnamic acid ester, monoolefins such as ethylene, propylene, butene and pentene, Examples include vinylidene chloride; monomers such as styrene and its derivatives, acrylonitrile, and methacrylonitrile, and two or more of these can be used.

  Polymerization initiators include, for example, water-soluble initiators such as potassium persulfate and ammonium peroxide, azo compounds such as azobisisobutyronitrile, lauroyl peroxide, and t-butylperoxypiparate, diacyl peroxide, and peroxyester And oil-soluble initiators such as peroxydicarbonate, and two or more of them can be used.

  Chain transfer agents include, for example, halogenated hydrocarbons such as trichlorethylene and carbon tetrachloride; mercaptans such as 2-meltcaptoethanol, octyl 3-meltcaptopropionate, and dodecyl mercaptan; aldehydes such as acetone and n-butyraldehyde Etc., and two or more of these can be used.

  The aqueous medium used in the present invention is water and other water-soluble polymerization aids (buffering agents, etc.), and is a medium in which an organic layer such as a vinyl chloride monomer is dispersed.

  In addition to the soap-free vinyl chloride resin latex, the adhesion aid of the present invention can contain an anti-aging agent, an antioxidant, an antiseptic, an antifungal agent, and the like, if necessary.

  The RFL adhesive treatment liquid of the present invention contains the above-mentioned adhesion assistant, an RFL liquid containing an aqueous solution of resorcin and formalin condensate, and rubber latex.

  The aqueous solution of resorcin and formalin condensate contained in the RFL solution is, for example, a resorcin such as 1,3-benzenediol, 1,5-benzenediol, bishydroxymethylphenol, bishydroxyalkylphenol such as bishydroxyethylphenol, and formalin. An aqueous solution of the condensate can be mentioned. These are produced by a basic catalyst such as sodium hydroxide, potassium hydroxide or ammonia, or an acid catalyst such as hydrochloric acid or sulfuric acid.

  The rubber latex contained in the RFL liquid is, for example, a vinylpyridine-styrene-butadiene copolymer latex, a modified latex obtained by modifying a vinylpyridine-styrene-butadiene copolymer latex with a carboxyl group, or a styrene-butadiene copolymer. Latex and its modified latex, acrylonitrile-butadiene rubber and its modified latex, natural rubber latex, chloroprene rubber latex, butyl rubber latex, acrylate copolymer latex, etc. In particular, it is desirable to contain a vinylpyridine-styrene-butadiene copolymer latex.

  The RFL liquid containing an aqueous solution of resorcin and formalin condensate and rubber latex can be obtained by mixing an aqueous solution of resorcin and formalin condensate and rubber latex in an arbitrary ratio.

  The RFL adhesive treatment liquid of the present invention is obtained by mixing and dispersing an adhesion assistant in an RFL liquid containing an aqueous solution of resorcin and formalin condensate and rubber latex. The mixing / dispersing method is not particularly limited, and examples thereof include mixing / dispersing with a stirring blade and mixing / dispersing with a homogenizer.

  The RFL adhesive treatment liquid of the present invention may contain an isocyanate compound, a blocked isocyanate compound, an epoxy compound, or the like as necessary.

  Examples of isocyanate compounds include polyisocyanates such as tolylene diisocyanate, m-phenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate, or compounds having two or more of these isocyanates and active hydrogen atoms, for example, And polyhydric alcohol-added polyisocyanate compounds obtained by reacting with trimethylolpropane yapentaerythritol and the like.

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

  Although it does not specifically limit as an epoxy compound, It is a polyepoxide compound which has two or more epoxy in a molecule | numerator, for example, polyhydric alcohols, such as ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethyleneglycol, and epichlorohydrin. Reaction products such as halogen-containing epoxides, reaction products of resorcin, bis (4-hydroxyphenyl) dimethylmethane, polyhydric phenols such as phenol / formaldehyde resin and the halogen-containing epoxides, and 3,4-epoxycyclohexene Examples thereof include epoxide, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexenecarboxylate, and bis (3,4-epoxy-6-methyl-cyclomethyl) adipate.

  These isocyanate compounds, blocked isocyanate compounds, and epoxy compounds may be used as fiber treatment agents, and the fibers may be directly diluted with an organic solvent in ethyl acetate or the like, coated and dried, or mixed and dispersed in an RFL adhesive treatment solution. May mix and disperse these compounds with a stirrer.

  Examples of the fiber to be treated with the RFL adhesive treatment liquid of the present invention include polyester fiber, nylon fiber, glass 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 immersing the fiber in the RFL adhesive treatment liquid of the present invention is not particularly limited, but 1) a method of impregnating and drying the fiber of the RFL adhesive treatment liquid of the present invention 2) isocyanate compound, blocked isocyanate A method in which a compound or an epoxy compound is previously diluted in an organic solvent such as ethyl acetate and immersed and dried in a fiber, and then the fiber is impregnated and dried with the RFL adhesive treatment liquid of the present invention. 3) Isocyanate compound, blocked isocyanate compound or epoxy compound Can be mixed and dispersed in the RFL adhesive treatment solution of the present invention and impregnated and dried into fibers.

  The fiber impregnated with the RFL adhesive treatment liquid of the present invention is subjected to a drying process for removing moisture at 80 to 150 ° C., and is then used to promote resinification of the RFL adhesion treatment liquid and chemical bonding with the fiber. Although it is preferable to perform heat treatment (baking) at a temperature of 0 ° C. or higher, there is no particular limitation on the baking method. Moreover, the fiber which does not need to perform a baking process does not need to perform this process.

  The rubber composition used in the rubber composition-fiber composite of the present invention is a raw material rubber and a secondary raw material comprising a filler, a plasticizer, a vulcanizing agent, a vulcanization accelerator, an antiaging agent, a processing aid and the like. It is a rubber compound obtained by kneading a product.

  The raw rubber is not particularly limited, but is an unsaturated rubber such as natural rubber (NR), styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber, halogenated butyl rubber, Examples include chlorosulfonated polyethylene (CSM), chlorinated polyethylene, hydrogenated nitrile rubber, ethylene propylene rubber, epichlorohydrin rubber, saturated rubber such as fluoro rubber, acrylic rubber, and silicone rubber. You may use together the rubber | gum of a seed | species or more.

  For example, in addition to fillers such as carbon black, mica, silica, clay, magnesium hydroxide, aluminum hydroxide, graphite, mica and ferrite, the auxiliary raw materials are paraffinic oil, naphthenic oil, aroma oil, soybean oil Vegetable oils 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, tetraethyl Vulcanization accelerators such as thiuram disulfide, morpholinodithiobenzothiazole, diphenylthiourea, diphenylguanidine, mercaptobenzothiazole, N-sulfenamide, zinc dimethyldicarbamate, and metal oxides such as magnesium oxide and lead oxide Accelerator, scorch inhibitor such as phthalic anhydride, nitrosodiphenylamine, anti-aging agent such as N-isopropyl N′-phenyl-p-phenylenediamine, 2,6-di-t-butylcatechol, mercaptobenzimidazole, thio Peptizers such as xylenol and dixyl disulfide, activators such as wax and stearic acid, terpene phenols, tackifiers such as murrosin and tall oil rosin, sodium bicarbonate, azodicarbonamide, p, p'-oxybis Examples thereof include foaming agents such as (benzenesulfonyl hydrazide), and there is no particular limitation on using these.

  The kneading of the raw rubber and the auxiliary raw material is not particularly restricted but is mixed and dispersed by a mixer such as an open roll, a pressure kneader, or a Banbury mixer.

  When the form of the fiber is a cord, a woven fabric, a sheet, etc., for example, the fiber is baked after being dipped in the RFL adhesive treatment liquid of the present invention that enhances the adhesion between the rubber composition and the fiber and dried to remove moisture. The fiber that needs to be treated is a fiber that has been subjected to a baking treatment) and the rubber composition, and the rubber composition is vulcanized to simultaneously bond the rubber composition and the fiber. You can get a body. When the fiber is short fiber, for example, the rubber composition is immersed in the RFL adhesive treatment liquid of the present invention, dried short fibers are kneaded and vulcanized to obtain a rubber composition. The rubber composition-fiber composite of the present invention can be obtained by simultaneously bonding the fiber and the fiber. Examples of the vulcanization method include press vulcanization, steam vulcanization, hot air vulcanization, UHF vulcanization, electron beam vulcanization, and molten salt vulcanization, and any method may be used.

  By molding the rubber composition-fiber composite of the present invention, a rubber composition-fiber composite molded body can be obtained. Examples of the molding method include calendering, extrusion molding, injection molding, and compression molding, and these are not particularly limited.

  The RFL adhesive treatment liquid of the present invention in which the adhesion aid of the present invention is mixed and dispersed in the RFL liquid is excellent in working environment, and is impregnated into a fiber and then dried, whereby the rubber composition-fiber composite of the present invention is obtained. The body is excellent in the initial adhesive strength between the rubber composition and the fiber, the adhesive strength after heat deterioration, and the adhesive strength after heat fatigue bending.

  The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited by these.

<Measurement method of average particle diameter>
The average particle size of the copolymer in the soap-free vinyl chloride latex was measured by adding water to adjust the concentration so that the laser transmittance was 75 to 85%. Using a diameter measuring device (LA920, manufactured by HORIBA, Ltd.), the median particle size was determined and taken as the average particle size.

<Measurement of initial adhesive strength of rubber composition-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. For the test piece, a tensile tester (Model RTM-500, manufactured by Orientec Co., Ltd.) was used to determine the peel force by a peel test between the vulcanized rubber composition and the fiber at a peel rate of 50 mm / min. did.

<Measurement of adhesive strength of rubber composition-fiber composite after heat resistance deterioration>
The rubber composition-fiber composite sheet was post-vulcanized at 175 ° C. for 2 hours in a gear oven, and the peel test of the rubber composition-fiber composite sheet was performed in the same manner as the initial adhesive strength, after heat resistance deterioration The adhesive strength was.

<Measurement of Adhesive Strength of Heat Resistant Bending Fatigue of Rubber Composition-Fiber Composite>
The rubber composition-fiber composite sheet was subjected to a thermal fatigue test 100,000 times at 100 ° C. and 300 rpm using a constant elongation bending fatigue tester (manufactured by Ueshima Seisakusho), and then the rubber composition-fiber composite sheet was peeled off. The test was performed in the same manner as the initial adhesive strength, and the adhesive strength after heat-resistant bending fatigue was determined.

Example 1
As shown in Table 1, 600.0 g of deionized water, 438.8 g of vinyl chloride monomer (97.5% by weight based on the total amount of charged monomers), potassium persulfate 2 as an initial charge in a 2.5 L autoclave .25 g was charged. The reaction mixture was stirred with a stirring blade so as to maintain a rotational speed of 120 rpm, and the reaction mixture was raised to 60 ° C. to initiate polymerization. 11.2 g of glycidyl methacrylate (2.5% by weight based on all charged monomers) was continuously added at a rate of 2.8 g / hr from the start of polymerization to 4 hours later, and the vinyl chloride monomer at a polymerization pressure of 60 ° C. The polymerization was stopped when the saturated vapor pressure decreased by 0.6 MPa to obtain an adhesion assistant (soap-free vinyl chloride resin latex). The average particle size was 0.45 μm.

実施例２
表１に示す通り、グリシジルメタクリレートの代わりにアリルグリシジルエーテル１１．２ｇ（全仕込み単量体に対して２．５重量％）とした以外は、実施例１と同様の方法により、接着助剤（ソープフリー塩化ビニル系ラテックス）を得た（平均粒子径：０．４５μｍ）。

Example 2
As shown in Table 1, in the same manner as in Example 1 except that 11.2 g of allyl glycidyl ether (2.5% by weight based on the total charged monomers) was used instead of glycidyl methacrylate, an adhesion assistant ( Soap-free vinyl chloride latex) was obtained (average particle size: 0.45 μm).

Example 3
As shown in Table 1, the initial charge was 393.8 g of vinyl chloride monomer (87.5% by weight based on the total charge monomer), and 45.0 g of vinyl acetate monomer (based on the total charge monomer). Except that it was changed to 10.0% by weight, an adhesion assistant (soap-free vinyl chloride resin latex) was obtained in the same manner as in Example 1 (average particle size: 0.40 μm).

Example 4
As shown in Table 1, 448.6 g of vinyl chloride monomer (99.7 wt% with respect to all charged monomers), 1.4 g of glycidyl methacrylate (0.3 wt% with respect to all charged monomers) Was added in the same manner as in Example 1 except that continuous addition was performed at 0.7 g / hr from the start of polymerization to 2 hours later (average particle size: 0). .50 μm).

Example 5
As shown in Table 1, 427.5 g of vinyl chloride monomer (95.0% by weight based on all charged monomers), 22.5 g of glycidyl methacrylate (5.0% by weight based on all charged monomers) Was added in the same manner as in Example 1 except that continuous addition was performed at 5.63 g / hr from the start of polymerization to 4 hours later (average particle size: 0). .31 μm).

Example 6
As shown in Table 1, 448.9 g of vinyl chloride monomer (99.76 wt% with respect to all charged monomers), 1.1 g of glycidyl methacrylate (0.24 wt% with respect to all charged monomers) Was added in the same manner as in Example 1 except that the addition was continued at 0.55 g / hr from the start of polymerization to 2 hours later (average particle size: 0. 0). 75 μm).

Example 7
<Preparation of RF solution>
16.6 g of resorcin, 14.7 g of formalin 37% aqueous solution (dry weight 5.4 g), 1.3 g of sodium hydroxide and 334.4 g of water were dissolved in a 0.5 liter beaker, and the mixture was heated at room temperature (25 ° C.) for 2 hours. After stirring and condensing using a magnetic stirrer, 366.0 g of RF liquid having a resin solid content of 6.4% by weight was obtained.

<Preparation of RFL solution>
Solid content, RF solution 36.0g and polyvinyl pyridine styrene butadiene rubber 100.0g RF liquid 366.0g and polyvinyl pyridine styrene butadiene rubber latex (Nippon Zeon, Nipol 2518GL) 250.0g The mixture was placed in a beaker equipped with a 1 liter stirrer and aged for about 20 hours while stirring to obtain 616.0 g of RFL solution having a solid content concentration of 20% by weight.

<Preparation of RFL adhesive treatment liquid>
200.0 g of RFL solution and an adhesion assistant (soap-free vinyl chloride latex) so that the solid content is 100.0 parts by weight of RFL resin and 20.0 parts by weight of the soap-free vinyl chloride resin prepared in Example 1. ) 19.1 g was placed in a 0.5 liter beaker and aged for 10 minutes while stirring with a magnetic stirrer. Then, 4.3 parts by weight of Vulcabond MDX (manufactured by Acros Chemical Co.) as an isocyanate compound was added and stirred for 20 minutes. After that, it was filtered through a 100 mesh wire netting to prepare an RFL adhesive treatment solution having a solid content concentration of 22% by weight.

<Treatment with RFL Adhesive Treatment Solution (Preparation of Tetron Fiber)>
Tetron cloth (Shikishima canvas, T-81) is immersed in the RFL adhesive treatment solution for 10 minutes, dried in a 140 ° C gear oven, and then subjected to a pressureless baking process for 2 minutes on an electric heat press at 240 ° C. And treated with an RFL adhesive treatment solution.

<Preparation of rubber composition>
Natural rubber was used as a raw rubber, and a natural rubber composition was prepared with a 12-inch roll by the following composition.

Natural rubber 100.0 parts by weight Zinc flower 5.0
Stearic acid 2.0
FEF carbon black 45.0
Process oil 5.0
N-oxydiethylene-2-benzothiazylsulfenamide 1.0
Sulfur 2.5
2,2,4-Trimethyl-1,2-dihydroquinoline polymer 1.0
1,3-diphenylguanidine 0.2
<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by sandwiching a tetron fiber treated with an RFL adhesive treatment solution with a natural rubber composition and press vulcanizing at 150 ° C. for 30 minutes. The rubber composition-fiber composite was evaluated for initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue. The results are shown in Table 2. As is apparent from Table 2, the obtained rubber composition-fiber composite (natural rubber composition-tetron fiber composite) has excellent initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue. It was.

実施例８〜１２
実施例７と同様にして、表２に示すとおりの実施例２〜６で調製した接着助剤（ソープフリー塩化ビニル系ラテックス）を用いたＲＦＬ接着剤処理液、ゴム組成物−繊維複合体を調製し、初期接着力、耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力を評価した。その結果を表２に示す。表２から明らかなように、得られたゴム組成物−繊維複合体（天然ゴム組成物−テトロン繊維複合体）の初期接着力や耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力が優れていた。

Examples 8-12
In the same manner as in Example 7, the RFL adhesive treatment liquid, rubber composition-fiber composite using the adhesion promoter (soap-free vinyl chloride latex) prepared in Examples 2 to 6 as shown in Table 2 were used. The initial adhesive strength, the adhesive strength after heat resistance deterioration, and the adhesive strength after heat resistance bending fatigue were evaluated. The results are shown in Table 2. As is apparent from Table 2, the obtained rubber composition-fiber composite (natural rubber composition-tetron fiber composite) has excellent initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue. It was.

Example 13
<Preparation of rubber composition>
A styrene-butadiene rubber (SBR) was used as a raw rubber, and an SBR composition was prepared with a 12-inch roll by the following composition.

SBR (JSR1502, manufactured by JSR) 100.0 parts by weight Zinc flower 3.0
Stearic acid 2.0
FEF carbon black 85.0
Process oil 20.0
N-oxydiethylene-2-benzothiazylsulfenamide 1.0
Sulfur 1.5
2,2,4-Trimethyl-1,2-dihydroquinoline polymer 1.0
1,3-diphenylguanidine 0.2
<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by sandwiching tetron fiber treated with RFL adhesive treatment liquid with SBR composition and press vulcanizing at 150 ° C. for 30 minutes. The initial adhesive strength, adhesive strength after heat deterioration and The adhesive strength after heat-resistant bending fatigue was evaluated. The results are shown in Table 3. As is apparent from Table 3, the obtained rubber composition-fiber composite (SBR composition-tetron fiber composite) has excellent initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue. It was.

実施例１４
＜ゴム組成物の調製＞
クロロプレンゴム（ＣＲ）を原料ゴムとし、以下の配合によりＣＲ組成物を１２インチロールで調製した。

Example 14
<Preparation of rubber composition>
A chloroprene rubber (CR) was used as a raw rubber, and a CR composition was prepared with a 12-inch roll by the following composition.

CR (R-10, manufactured by Tosoh Corporation) 100.0 parts by weight Zinc flower 5.0
Magnesium oxide 4.0
Stearic acid 1.5
FEF carbon black 40.0
Dioctyl adipate bis (2-ethylhexyl) 5.0
Octylated diphenylamine 2.0
N, N′-diphenyl-p-phenylenediamine 0.35
<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by sandwiching a tetron fiber treated with an RFL adhesive treatment solution with a CR composition and press vulcanizing at 150 ° C. for 30 minutes to obtain an initial adhesive strength, an adhesive strength after heat deterioration, and The adhesive strength after heat-resistant bending fatigue was evaluated. The results are shown in Table 3. As can be seen from Table 3, the rubber composition-fiber composite (CR composition-tetron fiber composite) obtained has excellent initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue. It was.

Example 15
<Preparation of rubber composition>
Chlorosulfonated polyethylene rubber (CSM) was used as a raw rubber, and a CSM composition was prepared with a 12-inch roll by the following composition.

CSM (Ectos (registered trademark) ET-8010, manufactured by Tosoh Corporation) 100.0 parts by weight Magnesium oxide 4.0
Stearic acid 1.5
SRF carbon black 40.0
Pentaerythritol 3.0
Dipentamethylene disulfide 0.2
<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by immersing a dismodule RE (manufactured by Sumitomo Bayer), which is an isocyanate compound, in a 5% solution diluted with ethyl acetate and drying Tetron fiber dried at 140 ° C. as a resin solid content. The Tetron fiber treated with the RFL adhesive treatment liquid prepared to be 100.0 parts by weight of the RFL resin and 20.0 parts by weight of the soap-free vinyl chloride resin prepared in Example 1 was sandwiched with the CSM composition, and 150 ° C. Was prepared by press vulcanization for 30 minutes and evaluated in the same manner as in Example 7. The results are shown in Table 3. As can be seen from Table 3, the rubber composition-fiber composite (CSM composition-tetron fiber composite) obtained has excellent initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue. It was.

Examples 16-19
<Preparation of RF solution>
Resorcin 11.0 g, formalin 37% aqueous solution 16.2 g (dry weight 6.0 g), sodium hydroxide 0.3 g and water 235.8 g were dissolved in a 0.5 liter beaker and heated at room temperature (25 ° C.) for 6 hours. After stirring and condensing using a magnetic stirrer, 266.0 g of RF liquid having a resin solid content of 6.5% by weight was obtained.

<Preparation of RFL solution>
266.0 parts by weight of RF solution and polyvinylpyridine / styrene / butadiene rubber latex (Nipol 2518FS, manufactured by Nippon Zeon Co., Ltd.) 247. The solid content is RF 17.3 g and polyvinylpyridine / styrene / butadiene rubber 100.0 g. 0 g and 74.0 g of water were added, and the mixture was placed in a beaker equipped with a 1 liter stirrer and aged for about 20 hours with stirring to obtain 587.0 g of RFL solution having a solid content concentration of 20% by weight.

<Preparation of RFL adhesive treatment liquid>
200.0 g of RFL solution and an adhesive aid (soap-free vinyl chloride resin) so that the solid content is 100.0 parts by weight of RFL resin and 20.0 parts by weight of the soap-free vinyl chloride resin prepared in Example 1. Latex) 19.1 g was placed in a 0.5 liter beaker and aged for 30 minutes while stirring with a magnetic stirrer to prepare an RFL adhesive treatment solution having a solid content concentration of 22% by weight.

<Treatment with RFL adhesive treatment solution (preparation of nylon fibers)>
Nylon cloth (Shikishima Canvas Co., Ltd., N-856) is immersed in the RFL adhesive treatment solution for 10 minutes, dried in a 140 ° C gear oven, and then subjected to a pressureless baking process on a 190 ° C electric heat press for 2 minutes. And treated with an RFL adhesive treatment solution.

<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite is prepared by sandwiching RFL adhesive treated fibers with natural rubber composition, SBR composition, CR composition, and CSM composition, respectively, and press vulcanizing at 150 ° C. for 30 minutes for initial adhesion. The strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 4. As is apparent from Table 4, the obtained rubber composition-fiber composite (natural rubber composition-nylon fiber composite, SBR composition-nylon fiber composite, CR composition-nylon fiber composite, CSM composition -Nylon fiber composite) had excellent initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue.

実施例２０〜２３
＜ＲＦＬ液の調製＞
固形分にして、ＲＦ２３．３重量部とポリビニルピリジン・スチレン・ブタジエンゴム１００．０重量部になるようにＲＦ液３６６.０ｇ及びポリビニルピリジン・スチレン・ブタジエンゴムラテックス（日本ゼオン社製、ニポール２５１８ＧＬ）２５０.０ｇを１リットルの攪拌機のついたビーカーに入れ、攪拌しながら約２０時間熟成し、固形分濃度２０重量％のＲＦＬ液６１６．０ｇを得た。

Examples 20-23
<Preparation of RFL solution>
Solid solution, RF solution 366.0g and polyvinyl pyridine styrene butadiene rubber latex (Nipol 2518GL, manufactured by Nippon Zeon Co., Ltd.) so that RF 23.3 parts by weight and polyvinyl pyridine styrene butadiene rubber 100.0 parts by weight 250.0 g was placed in a beaker equipped with a 1 liter stirrer and aged for about 20 hours with stirring to obtain 616.0 g of RFL solution having a solid content concentration of 20% by weight.

<Preparation of RFL adhesive treatment liquid>
200.0 g of RFL solution and an adhesive aid (soap-free vinyl chloride resin) so that the solid content is 100.0 parts by weight of RFL resin and 20.0 parts by weight of soap-free vinyl chloride resin prepared in Example 1 Latex) 19.1 g was placed in a 0.5 liter beaker and aged for 10 minutes while stirring with a magnetic stirrer, and then 4.3 parts by weight of Vulcabond MDX (manufactured by Acros Chemical Co.) as an isocyanate compound was added for 20 minutes. After stirring, the mixture was filtered through a 100-mesh wire mesh to prepare an RFL adhesive treatment solution having a solid content concentration of 21% by weight.

<Treatment with RFL adhesive treatment solution (preparation of glass fiber)>
A glass fiber cloth (manufactured by Kanebo Co., Ltd., KS4300UNT) was immersed in an RFL adhesive treatment solution for 10 minutes and then dried in a gear oven at 140 ° C. to obtain a treated fiber using the RFL adhesive treatment solution.

<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite is prepared by sandwiching RFL adhesive treated fibers with natural rubber composition, SBR composition, CR composition, and CSM composition, respectively, and press vulcanizing at 150 ° C. for 30 minutes for initial adhesion. The strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 5. As is apparent from Table 5, the obtained rubber composition-fiber composite (natural rubber composition-glass fiber composite, SBR composition-glass fiber composite, CR composition-glass fiber composite, CSM composition -Initial adhesive strength of the glass fiber composite), adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue were excellent.

比較例１
表６に示す通り、５重量％のラウリン酸アンモニウム（アニオン系界面活性剤）水溶液１８０．０ｇを重合開始の９０分後から３６０分後まで、４０ｇ／ｈｒで連続仕込みとし、実施例１の脱イオン水を４２０．０ｇとした以外は、実施例１と同様の方法で、接着助剤（界面活性剤を含む塩化ビニル系樹脂ラテックス）を得た（平均粒子径：０．４０μｍ）。

Comparative Example 1
As shown in Table 6, 180.0 g of a 5 wt% aqueous solution of ammonium laurate (anionic surfactant) was continuously charged at 40 g / hr from 90 minutes to 360 minutes after the start of polymerization. An adhesion assistant (a vinyl chloride resin latex containing a surfactant) was obtained in the same manner as in Example 1 except that the amount of ionic water was changed to 420.0 g (average particle size: 0.40 μm).

比較例２
表６に示す通り、塩化ビニル単量体を４４９．２ｇ全仕込み単量体に対して９９．８２重量％）、グリシジルメタクリレート０．８ｇ（全仕込み単量体に対して０．１８重量％）を重合開始〜２ｈｒ後まで０．４ｇ／ｈｒで連続添加とした以外は、実施例１と同様の方法により、接着助剤（ソープフリー塩化ビニル系樹脂ラテックス）を得た（平均粒子径：０．８７μｍ）。

Comparative Example 2
As shown in Table 6, vinyl chloride monomer was 449.2 g based on 99.82% by weight of all charged monomers) and glycidyl methacrylate was 0.8 g (0.18% by weight based on all charged monomers). Was added in the same manner as in Example 1 except that continuous addition was performed at 0.4 g / hr from the start of polymerization to 2 hours later (average particle size: 0). .87 μm).

Comparative Example 3
As shown in Table 6, 414.0 g of vinyl chloride monomer (92.0% by weight based on all charged monomers) and 36.0 g of glycidyl methacrylate (8.0% by weight based on all charged monomers) ) Was obtained in the same manner as in Example 1 except that continuous addition was performed at 9.0 g / hr from the start of polymerization to 4 hours later (average particle size). : 0.32 μm).

Comparative Example 4
As shown in Table 6, 369.0 g of vinyl chloride monomer (82.0% by weight with respect to all charged monomers), 45.0 g of vinyl acetate (10.0% by weight with respect to all monomers) In the same manner as in Example 1, except that 36.0 g of glycidyl methacrylate (8.0% by weight based on all charged monomers) was continuously added at 9.0 g / hr from the start of polymerization to 4 hours later. An auxiliary agent (soap-free vinyl chloride resin latex) was obtained (average particle size: 0.33 μm).

Comparative Example 5
As shown in Table 6, 449.4 g of vinyl chloride monomer was 99.85 wt% with respect to all charged monomers), and 0.67 g of glycidyl methacrylate (0.15 wt% with respect to all charged monomers). Was added in the same manner as in Example 1 except that the addition was continued at 0.33 g / hr from the start of polymerization to 2 hours later (average particle size: 1). 20 μm).

Comparative Example 6
With respect to 200.0 g of RFL liquid corresponding to 100.0 parts by weight of RFL resin having the same composition as in Example 7 in terms of solid content, without adding an adhesion assistant (soap-free vinyl chloride resin latex), An RFL adhesive treatment solution was prepared by putting 4.3 g of VALQUABOND MDX corresponding to 2.1 parts by weight into a 0.5 liter beaker, stirring with a magnetic stirrer for 20 minutes, and filtering with a 100 mesh wire net. Tetron fibers were immersed in this treatment solution for 10 minutes to remove moisture at 140 ° C., and then baked at 240 ° C. for 2 minutes to obtain treated fibers. This treated fiber and natural rubber composition were vulcanized and bonded to prepare a rubber composition-fiber composite, and the initial adhesive strength, the adhesive strength after heat deterioration and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 7. As is apparent from Table 7, the RFL adhesive treatment liquid containing no adhesion assistant was inferior to Example 7 in initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat bending fatigue.

比較例７
固形分にして実施例７と同一組成のＲＦＬ樹脂１００．０重量部とクロロスルホン化ポリエチレンが２０.０重量部になるようにＲＦＬ液及びクロロスルホン化ポリエチレンラテックス（ＣＳＭラテックス）の接着助剤（ＣＳＭ４５００（製鉄化学工業社（株）製）とバルカボンドＭＤＸ２．１重量部を加えたＲＦＬ接着処理液を調製し、テトロン繊維の処理を行い、この処理繊維と天然ゴム組成物を加硫接着し、ゴム組成物−繊維複合体を調製し、初期接着力、耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力を評価した。その結果を表７に示す。表７から明らかなように、ＣＳＭラテックスを接着助剤としたＲＦＬ接着剤処理液は、実施例７に比べ、初期接着力や耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力は劣っていた。

Comparative Example 7
Adhesion aid for RFL solution and chlorosulfonated polyethylene latex (CSM latex) so that the solid content is 100.0 parts by weight of RFL resin having the same composition as in Example 7 and 20.0 parts by weight of chlorosulfonated polyethylene ( An RFL adhesion treatment liquid to which CSM4500 (manufactured by Steel Manufacturing Chemical Co., Ltd.) and VALQUABOND MDX2.1 parts by weight was added was prepared, the tetron fiber was treated, and the treated fiber and the natural rubber composition were vulcanized and bonded. A rubber composition-fiber composite was prepared and evaluated for initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue, and the results are shown in Table 7. As is apparent from Table 7, CSM. Compared with Example 7, the RFL adhesive treatment liquid using latex as an adhesion aid was inferior in initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat bending fatigue.

Comparative Example 8
RFL with a solid content of 100.0 parts by weight of RFL resin having the same composition as in Example 7, an adhesion aid of Comparative Example 1 (vinyl chloride resin latex containing a surfactant) and 2.1 parts by weight of VALQUABOND MDX Prepare adhesive treatment solution, treat Tetron fiber, vulcanize and bond this treated fiber and natural rubber composition to prepare rubber composition-fiber composite, initial adhesive strength, adhesive strength after heat deterioration And the adhesive force after heat-resistant bending fatigue was evaluated. The results are shown in Table 8. As is clear from Table 8, compared with Example 7, the initial adhesive force, the adhesive force after heat deterioration and the adhesive force after heat-resistant bending fatigue of the rubber composition-fiber composite using Comparative Example 1 were inferior. .

比較例９
固形分にして、実施例７と同一組成のＲＦＬ樹脂１００.０重量部と比較例２のソープフリー塩化ビニル系樹脂が２０.０重量部になるようにＲＦＬ液及びグリシジルメタクリレート０．２重量％を含む接着助剤（ソープフリー塩化ビニル系樹脂ラテックス）とバルカボンドＭＤＸ２．１重量部を加えたＲＦＬ接着剤処理液を調製し、テトロン繊維の処理を行い、この処理繊維と天然ゴム組成物を加硫接着し、ゴム組成物−繊維複合体を調製し、初期接着力、耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力を評価した。その結果を表８に示す。表８から明らかなように、実施例７に比べ、比較例２を用いたゴム組成物−繊維複合体の初期接着力や耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力は劣っていた。

Comparative Example 9
The RFL solution and glycidyl methacrylate were 0.2% by weight so that the solid content was 100.0 parts by weight of RFL resin having the same composition as in Example 7 and 20.0 parts by weight of the soap-free vinyl chloride resin of Comparative Example 2. An RFL adhesive treatment solution containing 2.1 parts by weight of Vulcabond MDX and an adhesive aid containing soap (soap-free vinyl chloride resin latex) is prepared, the tetron fiber is treated, and the treated fiber and natural rubber composition are added. Sulfur bonding was performed to prepare a rubber composition-fiber composite, and initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 8. As is apparent from Table 8, compared with Example 7, the rubber composition-fiber composite using Comparative Example 2 was inferior in initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat bending fatigue. .

Comparative Example 10
Containing 120.0% by weight of RFL solution and glycidyl methacrylate so that the solid content is 100.0 parts by weight of RFL resin having the same composition as in Example 7 and 20.0 parts by weight of the soap-free vinyl chloride resin of Comparative Example 3 An RFL adhesive treatment solution containing 2.1 parts by weight of an adhesion assistant (soap-free vinyl chloride resin latex) and VALQUABOND MDX was prepared, treated with tetron fiber, and the treated fiber and natural rubber composition were vulcanized and bonded. Then, a rubber composition-fiber composite was prepared, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 8. As is clear from Table 8, the initial adhesive strength of the rubber composition-fiber composite using Comparative Example 3 was superior to that of Example 7, but the adhesive strength after heat-resistant deterioration and the adhesive strength after heat-resistant bending fatigue. Was inferior.

Comparative Example 11
The solid content was 100.0 parts by weight of RFL resin having the same composition as in Example 7 and 20.0 parts by weight of the soap-free vinyl chloride resin of Comparative Example 4 and 12% by weight of RFL solution and glycidyl methacrylate, acetic acid. An RFL adhesive treatment solution containing 2.0 parts by weight of a vinyl monomer (soap-free vinyl chloride resin latex) and 2.1 parts by weight of VALQUABOND MDX was prepared and treated with Tetron fiber. The treated fiber and natural rubber composition were vulcanized and bonded to prepare a rubber composition-fiber composite, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 8. As is clear from Table 8, the initial adhesive strength of the rubber composition-fiber composite using Comparative Example 4 was superior to that of Example 7, but the adhesive strength after heat deterioration and the adhesive strength after heat bending fatigue Was inferior.

Comparative Example 12
The solid content of RFL resin and glycidyl methacrylate 0.1% by weight so that 100.0 parts by weight of RFL resin having the same composition as in Example 7 and 20.0 parts by weight of the soap-free vinyl chloride resin of Comparative Example 5 were obtained. An RFL adhesive treatment solution containing 2.1 parts by weight of Vulcabond MDX and an adhesive aid containing soap (soap-free vinyl chloride resin latex) is prepared, the tetron fiber is treated, and the treated fiber and natural rubber composition are added. Sulfur bonding was performed to prepare a rubber composition-fiber composite, and initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 8. As is apparent from Table 8, compared with Example 7, the rubber composition-fiber composite using Comparative Example 5 was inferior in initial adhesive force, adhesive force after heat deterioration, and adhesive force after heat bending fatigue. .

Comparative Example 13
An RFL adhesive treatment liquid was prepared by adding 2.1 parts by weight of VALQUABOND MDX to an RFL liquid corresponding to 100 parts by weight of the RFL resin having the same composition as in Example 7 as a solid content. Then, the tetron fiber is processed using this, the treated fiber and the SBR composition are vulcanized and bonded, and a rubber composition-fiber composite is prepared. After the initial adhesive strength, the adhesive strength after heat deterioration, and the heat bending resistance The adhesive strength of was evaluated. The results are shown in Table 9. As is clear from Table 9, the RFL adhesive treatment liquid containing no adhesion assistant was inferior to Example 13 in terms of initial adhesion, adhesion after heat deterioration, and adhesion after heat bending fatigue.

比較例１４
ゴムをＳＢＲからＣＲに変更した以外は比較例１３と同様にしてゴム組成物−繊維複合体を調製し、初期接着力、耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力を評価した。その結果を表９に示す。表９から明らかなように、接着助剤を含まないＲＦＬ接着剤処理液は、実施例１４に比べ、初期接着力や耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力は劣っていた。

Comparative Example 14
A rubber composition-fiber composite was prepared in the same manner as in Comparative Example 13 except that the rubber was changed from SBR to CR, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 9. As is clear from Table 9, the RFL adhesive treatment liquid containing no adhesion assistant was inferior to Example 14 in initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat bending fatigue.

Comparative Example 15
An RFL adhesive treatment solution corresponding to 100.0 parts by weight of the RFL resin having the same composition as that of Example 7 in terms of solid content was prepared. Tetoron fiber was pretreated with Dismodule RE in the same manner as in Example 15 to prepare a CSM composition-tetron fiber composite, a rubber composition-fiber composite, initial adhesion, and adhesion after heat deterioration. The strength and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 9. As is clear from Table 9, compared to Example 15, the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue of the rubber composition-fiber composite composed of CSM and tetron fiber were inferior. .

Comparative Example 16
An RFL adhesive treatment solution corresponding to 100.0 parts by weight of RFL resin having the same composition as in Examples 16 to 19 was prepared. This was used to treat the nylon fiber, and the treated fiber and the natural rubber composition were vulcanized and bonded, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 10. As is apparent from Table 10, compared to Example 16, the initial adhesive force, the adhesive force after heat deterioration and the adhesive force after heat-resistant bending fatigue of the rubber composition-fiber composite composed of natural rubber and nylon fiber are inferior. It was.

比較例１７
ゴムを天然ゴムからＳＢＲに変更した以外は比較例１６と同様にしてゴム組成物−繊維複合体を調製し、初期接着力、耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力を評価した。その結果を表１０に示す。表１０から明らかなように、実施例１７に比べ、ＳＢＲとナイロン繊維からなるゴム組成物−繊維複合体の初期接着力や耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力は劣っていた。

Comparative Example 17
A rubber composition-fiber composite was prepared in the same manner as in Comparative Example 16 except that the rubber was changed from natural rubber to SBR, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue were evaluated. . The results are shown in Table 10. As is apparent from Table 10, compared to Example 17, the initial adhesive strength, the adhesive strength after heat deterioration and the adhesive strength after heat-resistant bending fatigue of the rubber composition-fiber composite composed of SBR and nylon fiber were inferior. .

Comparative Example 18
A rubber composition-fiber composite was prepared in the same manner as in Comparative Example 16 except that the rubber was changed from natural rubber to CR, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat bending fatigue were evaluated. . The results are shown in Table 10. As is clear from Table 10, compared to Example 18, the initial adhesive force, the adhesive strength after heat deterioration and the adhesive strength after heat-resistant bending fatigue of the rubber composition-fiber composite composed of CR and nylon fibers were inferior. .

Comparative Example 19
A rubber composition-fiber composite was prepared in the same manner as in Comparative Example 16 except that the rubber was changed from natural rubber to CSM, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat bending fatigue were evaluated. . The results are shown in Table 10. As is apparent from Table 10, compared to Example 19, the rubber composition-fiber composite composed of CSM and tetron fibers had inferior initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat-resistant bending fatigue.

Comparative Example 20
With respect to 200.0 g of RFL liquid corresponding to 100.0 parts by weight of RFL resin having the same composition as in Example 7 in solid content, without adding an adhesion assistant (soap-free vinyl chloride resin latex), On the other hand, 4.3 g of VALQUABOND MDX corresponding to 2.1 parts by weight was put into a 0.5 liter beaker, stirred for 20 minutes with a magnetic stirrer, and then filtered through a 100-mesh wire mesh to prepare an RFL adhesive treatment solution. In this treatment liquid, glass fibers were immersed for 10 minutes to obtain treated fibers from which moisture was removed at 140 ° C. This treated fiber and natural rubber composition were vulcanized and bonded to prepare a rubber composition-fiber composite, and the initial adhesive strength, the adhesive strength after heat deterioration and the adhesive strength after heat-resistant bending fatigue were evaluated. The results are shown in Table 11. As is clear from Table 11, compared to Example 20, the rubber composition-fiber composite composed of natural rubber and glass fiber was inferior in initial adhesive strength, adhesive strength after heat deterioration, and adhesive strength after heat bending fatigue. .

比較例２１
ゴムを天然ゴムからＳＢＲに変更した以外は比較例２０と同様にしてゴム組成物−繊維複合体を調製し、初期接着力、耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力を評価した。その結果を表１１に示す。表１１から明らかなように、実施例２１に比べ接着助剤（ソープフリー塩化ビニル系樹脂ラテックス）を含有しないＳＢＲとガラス繊維からなるゴム組成物−繊維複合体の初期接着力や耐熱劣化後の接着力及び耐熱屈曲疲労後の接着力は劣っていた。

Comparative Example 21
A rubber composition-fiber composite was prepared in the same manner as in Comparative Example 20 except that the rubber was changed from natural rubber to SBR, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat-resistant bending fatigue were evaluated. . The results are shown in Table 11. As is clear from Table 11, the initial adhesive strength of the rubber composition-fiber composite composed of SBR and glass fiber not containing an adhesion assistant (soap-free vinyl chloride resin latex) as compared with Example 21 and after heat resistance deterioration. The adhesive strength and the adhesive strength after heat-resistant bending fatigue were inferior.

Comparative Example 22
A rubber composition-fiber composite was prepared in the same manner as in Comparative Example 20 except that the rubber was changed from natural rubber to CR, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat bending fatigue were evaluated. . The results are shown in Table 11. As is clear from Table 11, the initial adhesive strength of the rubber composition-fiber composite composed of CR and glass fiber not containing an adhesion aid (soap-free vinyl chloride resin latex) as compared with Example 22 and after heat resistance deterioration. The adhesive strength and the adhesive strength after heat-resistant bending fatigue were inferior.

Comparative Example 23
A rubber composition-fiber composite was prepared in the same manner as in Comparative Example 20 except that the rubber was changed from natural rubber to CSM, and the initial adhesive strength, the adhesive strength after heat deterioration, and the adhesive strength after heat bending fatigue were evaluated. . The results are shown in Table 11. As is clear from Table 11, the initial adhesive strength of the rubber composition-fiber composite composed of CSM and glass fiber not containing an adhesion assistant (soap-free vinyl chloride resin latex) as compared with Example 23 and after heat resistance deterioration. The adhesive strength and the adhesive strength after heat-resistant bending fatigue were inferior.

  The rubber composition-fiber composite of the present invention uses the RFL adhesive treatment liquid of the present invention using the adhesion aid of the present invention, so that the initial adhesive force between the rubber composition and the fiber and adhesion after heat deterioration The rubber composition-fiber composite molded body of the present invention is used for tires such as automobile tires, motorcycle / bicycle tires, and solid tires for industrial vehicles. Various belts such as belts, toothed belts, conveyor belts, flat belts for power transmission, and industrial belts, rubber hoses for automobiles, industrial rubber hoses, air vanes for trucks and buses, air vanes for automobiles, railways It is used for a wide range of applications such as air blades for vehicles, air blades for industrial machinery, civil engineering and building sheets, and daily commodities for rubber footwear.

Claims (6)

Contains a copolymer containing vinyl chloride and 0.2 to 6% by weight of epoxy group-containing vinyl, does not contain a surfactant, and contains a soap-free vinyl chloride resin latex with an average particle size of 1.0 μm or less An RFL adhesive treatment liquid comprising: an adhesion assistant , and an RFL liquid containing an aqueous solution of resorcin and formalin condensate and rubber latex . 2. The RFL adhesive treatment liquid according to claim 1, wherein the epoxy group-containing vinyl contains an adhesion assistant which is glycidyl methacrylate or allyl glycidyl ether. The RFL adhesive treatment liquid according to claim 1 or 2, wherein the copolymer contains an adhesion assistant containing a carboxylic acid vinyl ester in addition to vinyl chloride and an epoxy group-containing vinyl. The RFL adhesive treatment liquid according to claim 3, wherein the vinyl carboxylate is vinyl acetate. Contains a copolymer containing vinyl chloride and 0.2 to 6% by weight of epoxy group-containing vinyl, does not contain a surfactant, and contains a soap-free vinyl chloride resin latex with an average particle size of 1.0 μm or less 5. The RFL adhesive treatment liquid according to claim 1, wherein the adhesion assistant is mixed and dispersed in an RFL liquid containing an aqueous solution of resorcin and formalin condensate and a rubber latex. Way . A rubber composition-fiber obtained by vulcanizing a treated fiber and a rubber composition obtained by impregnating a fiber with the RFL adhesive treatment solution according to any one of claims 1 to 4 A method for producing a composite .