JPH0369934B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a method for adhering aromatic polyamide fibers and rubber compounds. Conventional technology Generally, tires, rubber hoses, power transmission belts,
Industrial rubber products such as conveyor belts are reinforced using fibrous materials. Synthetic fibers are, for example,
Compared to natural fibers such as cotton, wool, and hemp, it has excellent properties such as being stronger, having a higher modulus of elasticity, and having better resistance to friction, and almost no dimensional change due to water or heat. Therefore, it is widely used as such reinforcing fiber material. In particular, in recent years, among synthetic fibers, polyamide-based and polyester-based synthetic fiber materials such as aliphatic polyamide fibers, aromatic polyamide fibers, and polyester fibers have been widely used as reinforcing fiber materials. Conventionally, in order to bond fibers and rubber compounds, it is widely known that a mixture of resorcinol/formalin resin and rubber latex, so-called resorcinol/formalin resin/rubber latex (hereinafter referred to as RFL), is used as an adhesive. According to this method, a certain degree of adhesive force can also be obtained between the synthetic fiber and the rubber compound. However, the adhesion performance between the reinforcing fiber material and rubber is an important factor that affects the performance of rubber products such as those mentioned above, and synthetic fibers generally have poor wettability with RFL, so the adhesion that can be obtained is Power is insufficient. Therefore, in general, various methods using RFL have been proposed in order to increase the adhesive strength between synthetic fibers and rubber compounds. For example, JP-A-49-
Publication No. 96048 proposes a method of using RFL, which is made by mixing chlorohydrin rubber latex and chloroprene rubber latex with resorcinol/formalin resin, in adhering polyamide fibers and chloroprene rubber. In Japanese Patent Application Laid-open No. 59-89375, chloroprene
Using RFL made of dichlorobutadiene copolymer latex and resorcinol/formalin resin,
A method of bonding rubber to fibers has been proposed. On the other hand, regarding rubber, in recent years, not only natural rubber, styrene/butadiene rubber, etc., but also highly saturated nitrile rubber, ethylene/propylene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, hychlorohydrin rubber, fluoro rubber, etc. Saturated or fully saturated rubbers have come into use in various fields, and such specialty rubbers are more difficult to bond with synthetic fibers. Therefore, regarding the adhesion between such rubber and fibers, Japanese Patent Application Laid-Open No. 61-207442 describes, for example, an epitaxial method when adhering highly saturated hydrocarbon rubber containing a nitrile group such as hydrogenated nitrile rubber to fibers. A method using RFL consisting of a halogen-containing polymer such as chlorohydrin polymer, chloroprene rubber, chlorosulfonated polyethylene, or chlorinated polyethylene and resorcinol/formalin resin has been proposed. However, compared to conventional aliphatic polyamide fibers and polyester fibers, aromatic polyamide fibers have a more inert surface and are significantly inferior in wettability to RFL. When a vulcanized adhesive composite is used in a high-temperature environment under harsh conditions where it is subjected to dynamic external forces such as bending, compression, and elongation, resulting in large shear between the fiber and rubber, the above-mentioned According to conventional bonding methods, the adhesion strength is insufficient, and as a result, peeling failure occurs at the interface between the fiber and rubber, and the product cannot have a long service life. characteristics are not fully utilized. Problems to be Solved by the Invention It is an object of the present invention to provide an adhesion method that can achieve significantly improved adhesion between aromatic polyamide fibers and rubber compared to conventional methods. Means for Solving the Problems The present invention provides a method for adhering aromatic polyamide fibers and rubber compounds.
A first step of treating aromatic polyamide fibers with resorcinol/formalin resin/halogen-containing polymer latex containing 45% by weight or more of halogen-containing polymer latex, and (b) isocyanate compound or epoxy compound 10
The second adhesive composition is treated with an adhesive composition containing 90 to 10% by weight of an adhesive rubber that is compatible with the rubber polymer in the rubber compound relative to 90% by weight.
It is characterized by including a process. In the method of the present invention, the resorcin/formalin resin used in the first step is conventionally known for adhesion between rubber and fibers, and usually, resorcin and formalin are mixed at a molar ratio of resorcin/formalin. It is an initial condensate obtained by condensation in the presence of a basic catalyst at a ratio of 1/3 to 3/1, and is usually used as an aqueous solution of 5 to 80% by weight. Further, the halogen-containing polymer latex having a halogen content of 45% by weight or more used in the method of the present invention includes, for example, vinyl chloride, chlorinated rubber, chlorinated polyethylene, dichlorobutadiene homopolymer, vinyl acetate, vinyl chloride, Examples include copolymers with vinylidene chloride, maleic anhydride, acrylic esters, methacrylic esters, acrylonitrile, vinyl ether compounds, ethylene, propylene, chloroprene, and the like. In particular, in the present invention, vinyl chloride, chlorinated rubber,
Or a mixture thereof is preferably used. In the method of the present invention, as a first step, aromatic polyamide fibers are mixed with a resorcinol/formalin resin comprising a mixture containing a resorcinol/formalin resin and a halogen-containing polymer latex having a halogen content of 45% by weight or more as described above. Aromatic polyamide fibers are treated with halogen polymer latex. Such resorcinol/formalin resin and halogen-containing polymer latex have high polarity and high affinity for aromatic polyamide fibers, and not only have excellent wettability, but also have excellent wettability with aromatic polyamide fibers. A highly cohesive adhesive layer is formed between the two. Therefore, a halogen-containing polymer having a halogen content of less than 45% by weight lacks the above effects and is not suitable for use in the present invention. In particular, resorcinol/formalin resin/halogen-containing polymer latex containing a halogen-containing polymer with a halogen content of less than 40% by weight can achieve strong adhesion between aromatic polyamide fibers and rubber. Can not do it. The above-mentioned resorcinol/formalin resin/halogen-containing polymer latex contains 50 to 50 parts of halogen-containing polymer per 100 parts by weight of resorcinol/formalin resin.
It is preferably contained in a range of 1000 parts by weight, and particularly preferably in a range of 200 to 800 parts by weight. In addition, the solid content concentration in resorcinol, formalin resin, and halogen-containing polymer latex is 10
It is preferably in the range of ~50% by weight. In the first step, the aromatic polyamide fibers are treated with the resorcinol/formalin resin/halogen-containing polymer latex by immersing the fibers in the latex and then subjecting them to heat treatment, if necessary. This heat treatment may be carried out at a temperature sufficient to cause reaction and fixation of the latex attached to the fibers, and is usually carried out at 100 to 270° C. for several minutes. On the other hand, even if aromatic polyamide fibers are treated with a latex containing only the halogen-containing polymer, effective adhesion cannot be obtained between the aromatic polyamide fibers and the rubber. In addition, as the halogen content in the halogen-containing polymer increases, the adhesive layer tends to become harder, and furthermore, as the amount of resorcinol/formalin resin/halogen-containing polymer latex attached to the aromatic polyamide fiber increases, There is a tendency to reduce the bending fatigue resistance of aromatic polyamide fibers. Therefore, in the present invention, the halogen content in the halogen-containing polymer used is preferably 50% by weight or less. In addition, it is desirable to reduce the amount of resorcinol, formalin resin, and halogen-containing polymer latex attached to aromatic polyamide fibers as much as possible. This may cause variations. Therefore, according to the method of the present invention, as the second step, an isocyanate compound or an epoxy compound 10
~90% by weight and 90 to 10% by weight of an adhesive rubber that is compatible with the adhered rubber polymer in the rubber compound, and by such treatment, resorcinol formalin resin・Even if the amount of halogen-containing polymer latex attached to aromatic polyamide fibers is small, the adhesive strength between the aromatic polyamide fibers and the adhered rubber will vary and the bending fatigue resistance of the aromatic polyamide fibers will decrease. Moreover, strong adhesion can be achieved without any problems. The isocyanate compound is not particularly limited, but for example, polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and polymethylene polyphenyl diisocyanate are preferably used. In addition, polyhydric alcohol-added polyisocyanates obtained by reacting such polyisocyanates with compounds having two or more active hydrogens in the molecule such as trimethylolpropane and pentaerythritol, and polyisocyanates with phenols and tertiary Blocked polyisocyanates obtained by blocking the isocyanate groups of polyisocyanates by reacting with blocking agents such as alcohols and secondary amines are also suitably used as polyisocyanate compounds. As the epoxy compound, a polyepoxy compound having two or more epoxy groups in the molecule is preferable, and therefore, for example, polyepoxy compounds such as polyhydric alcohols such as ethylene glycol, glycerin, sorbitol, and pentaerythritol, and polyalkylene glycols such as polyethylene glycol, etc. Reaction products with halogen-containing epoxy compounds such as epichlorohydrin, polyhydric phenols such as resorcinol, bis(4-hydroxyphenyl) dimethylethane, phenol/formamide resin, resorcinol/formamide resin, and phenolic resins and epichlorohydrin. A reaction product with a halogen-containing epoxy compound is preferably used. Isocyanate compounds and epoxy compounds are
When the rubber is vulcanized to the aromatic polyamide fiber, it becomes a resin and increases the cohesive force of the adhesive layer formed, and also reacts with the methylol groups of the resorcinol/formalin resin in the first step to form a strong adhesive layer. Form. Generally speaking, as the adherend rubber that is compatible with the adherend rubber, unvulcanized rubber that is the same as the adherend rubber or unvulcanized rubber that is similar from the viewpoint of chemical structure is used. Even if the unvulcanized rubber has a structure, the polarity of the adhesive rubber, that is,
When the solubility parameter (hereinafter referred to as SP value) is similar to that of the adhered rubber, it is compatible with the adhered rubber. It can be used as an adhesive rubber in an adhesive composition by blending it into the adhesive composition. Various methods are known for determining the above SP value, but
Usually determined by Small's method. This method can be used, for example, in J.Paint Technol., 42, 76
(1970); New Values of the Solubility
Described in Parameters from Vapor Pressure Data. In the method of the present invention, the rubber in the adhesive composition preferably has a SP value in the range of +1.0 to -1.0 with respect to the SP value of the attached rubber determined by the method of Small. When outside this range, the polarity difference between the adhered rubber and the adhered rubber is too large, resulting in poor compatibility with the adhered rubber, making it difficult to achieve strong adhesion between the aromatic polyamide fiber and the rubber. I can't. In the present invention, the adhesive composition contains 10 to 90% by weight of an isocyanate compound or an epoxy compound.
In contrast, the rubber compound contains 90 to 10% by weight of adhesive rubber that is compatible with the rubber polymer in the rubber compound. isocyanate compound or epoxy compound,
When the adhesive rubber is outside the above range, strong adhesion cannot be obtained between the aromatic polyamide fiber and the rubber compound. The adhesive composition used in the second step is usually a solution-type adhesive made by dissolving an isocyanate compound or an epoxy compound and an adhesive rubber that is compatible with the rubber polymer in the rubber compound in an appropriate organic solvent. used as an agent. The above organic solvent is not particularly limited, but usually includes aromatic hydrocarbons such as benzene, xylene, and toluene, aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and amyl acetate. is preferably used. Although the solid content concentration in such a solvent-based adhesive is not particularly limited, it is usually preferably in the range of 10 to 50% by weight. The treatment of the aromatic polyamide fibers with the adhesive composition in the second step is also carried out by immersing the fibers in the adhesive composition and then subjecting them to heat treatment, if necessary. This heat treatment may be carried out at a temperature sufficient to react and fix the adhesive composition attached to the fibers, and is usually carried out at a temperature of 250° C. or lower for several minutes. According to the present invention, the adhesive composition includes natural rubber, styrene-butadiene rubber,
When a halogen-free rubber such as acrylonitrile-butadiene rubber is used, it is preferable to further contain chlorinated natural rubber in addition to these adhesive rubbers. Such an adhesive composition has high compatibility with the resorcinol, formalin resin, and halogen-containing polymer attached to the aromatic polyamide fiber in the first step, and provides even stronger adhesion between the aromatic polyamide fiber and the rubber. Achieve. The amount of such chlorinated natural rubber in the adhesive composition is
The weight ratio of chlorinated natural rubber is 10 to 100 parts by weight.
Particularly preferred is a range of 1000 parts by weight. In this way, by further containing chlorinated natural rubber in the adhesive composition in addition to the adhered rubber, the compatibility of the adhesive composition with the resorcinol, formalin resin, and halogen-containing polymer can be further improved. Not only can the adhesive strength be increased, but also the cohesive force of the formed adhesive layer can be further increased to achieve stronger adhesion. The adhesive composition usually contains a rubber compound or rubber adhesive, such as carbon black, silica, fillers, softeners, anti-aging agents, zinc white, sulfur, sulfur compounds, nitroso compounds, etc., as appropriate. It may contain additives such as a vulcanizing agent and a vulcanization accelerator. Further, according to the method of the present invention, prior to the first step, the aromatic polyamide fiber is treated with isocyanate,
It can be treated with a solution of an epoxy compound or a mixture thereof. This treatment can also be carried out by immersing the aromatic polyamide fiber in the above solution and, if necessary, subjecting it to heat treatment to fix the above compound to the fiber. As the polyisocyanate and epoxy compound used in this pretreatment, those listed above can be used as appropriate. Such treatment activates the surface of the aromatic polyamide fiber and increases the wettability of the fiber with the resorcinol/formalin resin/halogen-containing polymer latex in the first step. The aromatic polyamide fibers treated as described above are then brought into close contact with a rubber compound and vulcanized and bonded under the usual processing conditions known for this rubber compound. The method of the present invention can be applied to adhered rubbers such as, but not limited to, natural rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, chlorinated polyethylene, and chlorosulfonated rubber. It can be applied to polyethylene, chlorohydrin rubber, fluoro rubber, etc. Particularly suitable are natural rubber, styrene-butadiene rubber, chloroprene rubber and acrylonitrile-butadiene rubber. Such rubbers can be filled with various reinforcing fillers, which are known as conventional rubber compounds, depending on the case.
It may contain appropriate amounts of anti-aging agents, plasticizers, vulcanization aids, processing aids, and the like. Effects of the Invention As described above, according to the method of the present invention, in the first step, aromatic polyamide fibers are treated with resorcinol.
Treated with a formalin resin/halogen-containing polymer latex, and then, as a second step, treated with an adhesive composition containing an isocyanate compound or an epoxy compound and an adhesive rubber that is compatible with the polymer in the rubber compound. By doing so, aromatic polyamide fibers can be firmly vulcanized and bonded to various rubber compounds. Therefore, the method of the present invention is suitable for adhering fibers as reinforcing bodies for various rubbers in dynamic products such as power transmission belts, conveyor belts, tires, and the like. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. Rubber and latex used in the examples below,
Their preparation will be explained. Polyvinyl chloride latex (PVC latex) Zeon 150X50 manufactured by Zeon Corporation, solid content 48% by weight, polyvinyl chloride chlorine content 57% by weight, SP value 9.7. Chlorinated rubber latex Asahi Denka Co., Ltd. with chlorine content of 65% by weight and SP value of 9.5
Prepare a mixture by adding 30 parts of chlorinated rubber CR-150 to 60 parts of toluene, add this to water mixed with 100 parts of water and 1.4 parts of emulsifier (aerosol OTR), and mix for 5 minutes with a homo mixer. and obtained latex. Solid content 20% by weight. Chloroprene rubber latex Chloroprene rubber latex manufactured by Denki Kagaku Kogyo Co., Ltd.
LV-60, solid content 50% by weight, chlorine content of chloroprene rubber 41% by weight, SP value 9.2. Chlorosulfonated polyethylene latex Chlorosulfonated polyethylene latex manufactured by Seitetsu Kagaku Kogyo Co., Ltd., solid content 40% by weight, chlorine content of chlorosulfonated polyethylene 25% by weight, SP value 9.1. Natural rubber latex Solid content 60% by weight, natural rubber SP value 8.3. Acrylonitrile/butadiene rubber (nitrile rubber) Nipol1043, Nitrile rubber manufactured by Nippon Zeon Co., Ltd., SP value
9.7. Chloroprene rubber Neoprene WRT manufactured by Showa Denko K.K., SP value 9.2. Isocyanate Compound As the isocyanate compound, Millionate MR (polymethylene polyphenyl polyisocyanate) manufactured by Nippon Polyurethane Kogyo Co., Ltd. or PAPI manufactured by Kasei Upjiyon Co., Ltd. was used. Epoxy compound Denacol EX313 (glycerol polyglycidyl ether) manufactured by Nagase Chemical Industries, Ltd. Chlorinated natural rubber CR-150 manufactured by Asahi Denka Co., Ltd., chlorine content 65% by weight, SP
Value 9.5. Moreover, in the obtained adhesive, the peeling state is shown below. F Fiber fracture F-A Fiber-adhesive interface fracture A Adhesive fracture A-R Adhesive-rubber interface fracture R Rubber cohesive fracture example 1 Aromatic polyamide fiber cord (Teijin Ltd. Technora, 1500D /1×3) was immersed in the treatment solution (a) having the composition shown in Table 1, and then heat-treated at 200° C. for 2 minutes. Next, when Example Formulation A and Comparative Example Formulation C were used, after immersing in the treatment liquid (b),
Heat treatment was performed at ℃ for 2 minutes. Each of the fiber cords treated as described above was brought into close contact with a sheet made of unvulcanized rubber compound 1 described below, and then vulcanized at 150° C. for 30 minutes to obtain an adhesive. Unvulcanized rubber compound 1 Natural rubber 100 parts Zinc white 5 parts Stearic acid 2 parts Sulfur 2.5 parts FEF carbon black 45 parts Process oil 5 parts N-oxydiethylene-2-benzothiazyl sulfenamide 1 part 2,2, 4-Trimethyl-1,2-dihydroquinoline 0.2 parts The thus obtained adhesive was measured for 180° peel adhesive strength between the fiber cord and the rubber using a peel tester at a peel rate of 100 mm/min. The results are shown in Table 1. Example 2 The same aromatic polyamide fiber cord as in Example 1 was immersed in each of the treatment liquids (a) having the compositions shown in Table 2, heat treated at 200°C for 2 minutes, and then treated with formulation A in Table 1 above. After being immersed in the treatment solution (b) described in 1., it was heat treated at 200°C for 2 minutes. Each of the fiber cords treated as described above was brought into close contact with the sheet of unvulcanized rubber compound 1, and then vulcanized at 150° C. for 30 minutes to obtain an adhesive. Regarding this adhesive, the peeling speed was measured using a peel tester.
The 180° peel adhesion between the fiber cord and rubber was measured at 100 mm/min. The results are shown in Table 2.

【table】

[Table] Also, the above formulation A as an example according to the present invention
Based on the results of the treatment with the above formulation D and the treatment with the above formulations E, F and G as comparative examples, the halogen content of the halogen-containing polymer in the treatment liquid (a) and the adhesive strength of the obtained adhesive Figure 1 shows the relationship between After treating the aromatic polyamide fiber with RFL containing polyvinyl chloride latex or chlorinated rubber latex, it is treated with an adhesive composition containing an isocyanate compound and natural rubber as an adhesive rubber, and this is added to a natural rubber compound. It is shown that extremely high adhesion strengths can be achieved by sulfur bonding. Example 3 The same aromatic polyamide fiber cord as in Example 1 was immersed in each of the treatment liquids (a) having the compositions shown in Table 3, and then heat treated at 200°C for 2 minutes.
After being immersed in the treatment solution (b) having the composition shown in Table 3, it was heat treated at 200°C for 2 minutes. Each of the fiber cords treated as described above was brought into close contact with a sheet consisting of the unvulcanized rubber compound 1 and vulcanized rubber compounds 2 and 3 shown below, and then vulcanized at 150°C for 30 minutes. An adhesive was obtained. Unvulcanized rubber compound 2 Neoprene WRT 100 parts Magnesium oxide 4 parts Zinc oxide 5 parts SRF carbon black 40 parts 2-mercaptoimidazoline 0.5 parts N,N'-di-β-naphthyl-p-phenylenediamine 0.5 parts 2, 2,4-trimethyl-1,2-dihydroquinoline 0.5 parts Process oil 10 parts Stearic acid 0.5 parts Unvulcanized rubber compound 3 Nitrile rubber 100 parts Zinc white No. 1 5 parts Stearic acid 1 part Sulfur Yellow 0.5 parts SRF carbon black 40 parts Tetramethylthiuram disulfide 2 parts Mercaptobenzothiazole 0.5 parts The peel rate of this adhesive was measured using a peel tester.
The 180° peel adhesion between the fiber cord and rubber was measured at 100 mm/min. The results are shown in Table 3. In addition, the SP value of the adhered rubber in the rubber compound,
When an adhesive composition containing natural rubber or nitrile rubber is used as the adhesive rubber, the relationship between the adhesive strength between the aromatic polyamide fiber and the adhered rubber in the resulting adhesive is shown in FIG. If aromatic polyamide fibers are treated with the above Example Formulation A using an adhesive composition containing natural rubber (SP value 8.3), when the adhered rubber is natural rubber,
A strong bond is obtained between the fiber and natural rubber.
Similarly, the adhered rubber is chloroprene rubber (SP value
9.2), the SP value of chloroprene rubber is close to that of natural rubber, and the difference is 0.9, so strong adhesion can be obtained between the fibers and chloroprene rubber.

[Table] However, the adhered rubber is nitrile rubber (SP value 9.7)
If so, the amount of natural rubber contained in the adhesive rubber
Since the difference from the SP value is as large as 1.4, strong adhesion cannot be obtained between the fiber and the nitrile rubber. On the other hand, if aromatic polyamide fibers are treated with the above formulation H using an adhesive composition containing nitrile rubber (SP value 9.7), if the adhered rubber is natural rubber, the difference in SP value from the nitrile rubber will be reduced. is large, so
It is not possible to obtain strong adhesion between fibers and natural rubber. However, when the adhered rubber is chloroprene rubber or nitrile rubber, the SP value of these adhered rubbers is the same as or close to that of the nitrile rubber that is the adhesive rubber, so there is a gap between the fibers and these adhered rubbers. Strong adhesion can be obtained. Example 4 The same aromatic polyamide fiber cord as in Example 1 was immersed in the treatment solution (a) having the composition shown in Table 4, then heat treated at 200°C for 2 minutes, and then the same aromatic polyamide fiber cord as in Example 1 was immersed in the treatment solution (a) having the composition shown in Table 4. 200℃ after immersion in treatment solution (b)
The sample was heat-treated for 2 minutes. Each of the fiber cords treated as described above was brought into close contact with each of the sheets made of the unvulcanized rubber compound 1, and then vulcanized at 150° C. for 30 minutes to obtain an adhesive. Regarding this adhesive, the peeling speed was measured using a peel tester.
The 180° peel adhesion between the fiber cord and rubber was measured at 100 mm/min. The results are shown in Table 4.

[Table] In addition, aromatic polyamide fibers were treated in the same manner as above, except that the weight ratio of adhesive rubber to isocyanate compound or epoxy compound in treatment liquid (b) was changed. It was vulcanized and adhered to a sheet made of sulfur rubber compound 1. FIG. 3 shows the relationship between the adhesive rubber/isocyanate compound or epoxy compound weight ratio in the treatment liquid (b) and the adhesive force between the aromatic polyamide fiber and the adhered rubber in the obtained adhesive. Example 5 The same aromatic polyamide fiber cord as in Example 1 was treated with a treatment solution (a) according to formulation A having the composition shown in Table 1.
After being immersed in water, heat treated at 200℃ for 2 minutes, then
After immersing natural rubber in a treatment solution (b) prepared by adding a predetermined amount of chlorinated natural rubber, it was heat-treated at 200°C for 2 minutes. Each of the fiber cords treated as described above was brought into close contact with each of the sheets made of the unvulcanized rubber compound 1, and then vulcanized at 150° C. for 30 minutes to obtain an adhesive. Regarding this adhesive, the peeling speed was measured using a peel tester.
The 180° peel adhesion between the fiber cord and rubber was measured at 100 mm/min. The results are shown in Figure 4. It has been shown that by adding a predetermined amount of chlorinated natural rubber to natural rubber in the adhesive composition, the adhesive force between the aromatic polyamide fiber and the adhered rubber is further improved. Example 6 The same aromatic polyamide fiber cord as in Example 1 was immersed in the pretreatment liquid (c) having the composition shown in Table 5, and then heat-treated at 200°C for 2 minutes, followed by formulation A in Example 1. In the same manner as above, process liquid (a) and
(b), and heat treated at 200°C for 2 minutes. Each of the fiber cords treated as described above was brought into close contact with each of the sheets made of the unvulcanized rubber compound 1, and then vulcanized at 150° C. for 30 minutes to obtain an adhesive. Regarding this adhesive, the peeling speed was measured using a peel tester.
The 180° peel adhesion between the fiber cord and rubber was measured at 100 mm/min. The results are shown in Table 5.

【table】 [Brief explanation of drawings]

Figure 1 is a graph showing the relationship between the chlorine content of the chlorine-containing polymer in resorcinol/formalin resin/chlorine-containing polymer latex and the adhesive strength between aromatic polyamide fibers and natural rubber. FIG. 3 is a graph showing changes in adhesive force between aromatic polyamide fibers and adherent rubber when using adherent rubbers and adhesive rubbers having various SP values. A graph showing the relationship between the weight ratio of an isocyanate compound or an epoxy compound and the adhesive force between an aromatic polyamide fiber and an adhered rubber,
FIG. 4 is a graph showing the influence of the blending of chlorinated natural rubber in the adhesive composition on the adhesive force between aromatic polyamide fibers and adhered rubber.

Claims (1)

[Claims] 1. A method for bonding aromatic polyamide fibers and a rubber compound, in which the aromatic polyamide fibers are bonded to (a) a resorcinol/formalin resin and a halogen content.
A first step of treating with a resorcinol/polymarin resin/halogen-containing polymer latex containing 45% by weight or more of a halogen-containing polymer latex, and (b) an isocyanate compound or epoxy compound 10
90% by weight of an adhesive rubber having compatibility with the adhered rubber polymer in the rubber compound.
A method for adhering aromatic polyamide fibers and a rubber compound, the method comprising a second step of treating with an adhesive composition containing 10% by weight. 2. The method of bonding aromatic polyamide fibers and a rubber compound according to claim 1, wherein the adhesive rubber has a solubility parameter in the range of +1.0 to -1.0 of the solubility parameter of the adhered rubber. 3. The method of bonding aromatic polyamide fibers and a rubber compound according to claim 1, wherein the adhesive composition contains chlorinated natural rubber. 4. The method of adhering aromatic polyamide fibers and a rubber compound according to claim 1, wherein the aromatic polyamide fibers are treated with an isocyanate compound or an epoxy compound prior to the first step.