JPH02170831A - Bonding of aromatic polyamide fiber and rubber compound - Google Patents

Abstract

PURPOSE:To improve the adhesivity in the bonding of an aromatic polyamide fiber to a rubber compound by treating the aromatic polyamide fiber with a specific latex of a resorcinol-formaldehyde resin and a halogen-containing polymer and with a specific adhesive composition. CONSTITUTION:An aromatic polyamide fiber is firmly bonded to a rubber compound by (1) treating the aromatic polyamide fiber with a latex of resorcinol- formaldehyde resin and a halogen-containing polymer and containing 100 pts.wt. of a resorcinol-formaldehyde resin produced by condensing resorcinol with formaldehyde in the presence of a basic catalyst and preferably 200-800 pts.wt. of a halogen-containing polymer, (2) treating the treated fiber with an adhesive composition produced by compounding 100 pts.wt. of a bonding rubber compatible to the adherend rubber polymer of the rubber compound with 1/5 pts.wt. of a methylene acceptor (e.g. resorcinol) and 1-10 pts.wt. of a methylene donor (e.g. hexamethylenetetramine), (3) closely contacting the treated fiber with a rubber compound and (4) vulcanizing the rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for adhering aromatic polyamide fibers and rubber compounds.

Industrial rubber products such as tires, rubber hoses, power transmission belts, and conveyor belts are generally reinforced using fiber materials. Synthetic fibers are generally stronger and have a higher modulus of elasticity than natural fibers such as cotton, wool, and hemp.
It is widely used as such a reinforcing fiber material because it has excellent properties such as excellent resistance to friction and almost no dimensional change due to water or heat. In particular, in recent years, among synthetic fibers, aliphatic polyamide fibers,
Polyamide-based and polyester-based synthetic fiber materials, such as aromatic polyamide fibers and polyester fibers, are often used as reinforcing fiber materials.

Conventionally, in order to bond fibers and rubber compounds, a mixture of resorcinol/formalin resin and rubber latex,
A method using so-called resorcinol formalin resin rubber latex (hereinafter referred to as RF L) as an adhesive is widely known, and according to this method, a certain degree of adhesion can be achieved between synthetic fibers and rubber compounds. You can gain power. 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. Generally, synthetic fibers have poor wettability with respect to RFL, so the adhesion that can be obtained Power is insufficient.

Therefore, various methods using RFL have been proposed in the past in order to improve the bonding strength between synthetic fibers and rubber compounds. For example, Japanese Patent Application Laid-Open No. 49-96048 proposes a method of using RFL made by mixing chlorohydrin rubber latex and chloroprene rubber latex with resorcinol/formalin resin to bond polyamide fibers and chloroprene rubber. There is.

JP-A-59-89375 proposes a method of bonding rubber to fibers using RFL made of chloroprene-dichlorobutadiene copolymer latex and resorcinol-formalin resin.

On the other hand, regarding rubber, in recent years, not only natural rubber, styrene/butadiene rubber, etc., but also highly 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, how to adhere a highly saturated hydrocarbon rubber containing a nitrile group, such as hydrogenated nitrile rubber, to fibers. Chlorhydrin polymer, chloroprene rubber, chlorosulfonated polyethylene,
A method using RFL consisting of a halogen-containing polymer such as chlorinated polyethylene and a 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 RFL wettability. When a vulcanized adhesive composite is used in a high-temperature environment and under harsh conditions where it is subjected to dynamic external forces such as bending, compression, and elongation, resulting in large shear between fibers and rubber, as described above, 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. Characteristics are not fully utilized.

(iii) An object of the present invention is to provide an adhesion method that can achieve adhesion strength between aromatic polyamide fibers and rubber that is significantly improved compared to conventional methods.

1. The present invention for increasing the fortune of 5 is a method of adhering aromatic polyamide fibers and a rubber compound, in which aromatic polyamide fibers are bonded with (al resorcinol/formalin resin and halogen-containing polymer latex having a halogen content of 45% by weight or more). A first step of treating aromatic polyamide fibers with a resorcinol/formalin resin/halogen-containing polymer latex containing the mixture, and ('b) determining compatibility with the methylene acceptor, methylene donor, and the rubber polymer in the rubber compound. In the method of the present invention, the resorcinol/formalin resin used in the first step has conventionally been used to treat rubber and fibers. It is known for its adhesion with resorcin and formalin, and is usually used at a molar ratio of resorcin/formalin of 1/1.
It is an initial condensate obtained by condensation in the presence of a basic catalyst at a ratio of 3 to 3/1, and is usually used as an aqueous solution of 5 to 80% by weight.

Furthermore, the halogen content used in the method of the present invention is 4
As a halogen-containing polymer latex containing 5% by weight or more,
For example, vinyl chloride, chlorinated rubber, chlorinated polyethylene, dichlorobutadiene homopolymers, vinyl acetate, vinyl chloride, vinylidene chloride, maleic anhydride, acrylic esters, methacrylic esters, acrylonitrile, vinyl ether compounds, ethylene, propylene , copolymers with 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 containing 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.

In such a resorcinol/formalin resin/halogen-containing polymer latex, the halogen-containing polymer has high polarity,
It not only has high affinity and compatibility with aromatic polyamide fibers and has excellent wettability, but also forms an adhesive layer with high cohesive strength with aromatic polyamide fibers. 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. especially,
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. I can't.

The resorcinol/formalin resin/halogen-containing polymer latex preferably contains a halogen-containing polymer in the range of 50 to 1000 parts by weight, particularly 200 to 800 parts by weight, per 100 parts by weight of the resorcinol/formalin resin.
The content is preferably within the range of parts by weight. Further, the solid content concentration in the resorcinol/formalin resin/halogen-containing polymer latex is preferably in the range of 10 to 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 react and fix the latex attached to the fibers (usually, the treatment may be 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. Additionally, it is desirable to reduce the amount of adhesion of resorcinol, formalin resin, and halogen-containing polymer latex to aromatic polyamide fibers. This may cause variations.

Therefore, according to the method of the present invention, as a second step, treatment is performed with an adhesive composition containing a methylene acceptor, a methylene donor, and an adhesive rubber that is compatible with the adhered rubber polymer in the rubber compound. However, through such treatment, even if the amount of resorcinol/formalin resin/halogen-containing polymer latex attached to the aromatic polyamide fiber is small, variations in adhesive strength and aromatic Strong adhesion can be achieved without reducing the bending fatigue resistance of polyamide fibers.

Examples of the methylene acceptor include resorcinol, m
-Aminophenol, m-disubstituted benzenes such as m-cresol, and examples of the methylene donor include hexamethylenetetramine, methylolmelamine, and the like.

As the adhered rubber that is compatible with the adhered rubber, - For boat fishing, unvulcanized rubber that is the same as the adhered rubber or unvulcanized rubber that is similar from the viewpoint of chemical structure, but different Even if an unvulcanized rubber has a chemical structure, if the polarity of the adhesive rubber, that is, the solubility parameter (hereinafter referred to as SP value) is similar to that of the adhered rubber, it is compatible with the adhered rubber. Therefore, it can be used as an adhesive rubber in an adhesive composition by previously blending a suitable vulcanized side into the adherend rubber compound according to the adhesive rubber to be used.

Although various methods are known for determining the SP value, the SP value is usually determined by the Sma 11 method. This method is described, for example, in 'J, Palnt Technol, +
42+ 76 (1970); New Values
of the 5olability Parameter
ters from Vapor Pressure
It is described in Data.

In the method of the present invention, the rubber in the adhesive composition preferably has an SP value in the range of +1.0 to -1.0 with respect to the SP value determined by the method of Sma 11 of the adhered rubber. . 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 above-mentioned adhesive composition has a bonding rubber of 100%
It contains 115 parts by weight of methylene acceptor and 1 to 10 parts by weight of methylene donor. When the amount of methylene acceptor and methylene donor relative to the adhered rubber is outside the above range, strong adhesion between the aromatic polyamide fiber and the rubber compound cannot be obtained.

The adhesive composition used in the second step is usually a solution prepared by dissolving a methylene acceptor, a methylene donor, and an adhesive rubber that is compatible with the rubber polymer in the rubber compound in an appropriate organic solvent. Used as mold adhesive. The organic solvents mentioned above are not particularly limited, but include:
Usually, 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 are preferably used. Although the solid content concentration in such a solvent-based adhesive is not particularly limited, it is usually 10
A range of 50% by weight is preferred.

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.
The treatment may be carried out for several minutes at a temperature of 0.degree. C. or lower.

According to the present invention, when a halogen-free rubber such as natural rubber, styrene-butadiene rubber, or acrylonitrile-butadiene rubber is used as the adhesive rubber, the adhesive composition further contains chlorinated natural rubber in addition to these adhesive rubbers. It is preferable to contain. 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 chlorinated natural rubber blended in the adhesive composition is particularly preferably such that the weight ratio of chlorinated natural rubber is in the range of 10 to 1000 parts by weight based on 100 parts by weight of the adhered rubber.

In this way, by further containing chlorinated natural rubber in addition to the adhered rubber in the adhesive composition, the compatibility of the adhesive composition with the resorcinol, formalin resin, and halogen-containing polymer is increased. Not only this, but also the cohesive force of the formed adhesive layer can be further increased to achieve stronger adhesion.

The adhesive composition is usually 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.

Furthermore, according to the method of the present invention, prior to the first step, the aromatic polyamide fibers can be treated with a solution of an isocyanate, an epoxy compound, or a mixture thereof.

In this treatment, the aromatic polyamide fibers are immersed in the above solution, and if necessary, heat-treated to fix the compound to the fibers.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. Also,
Such polyisocyanates include trimethylolpropane,
2 active hydrogens in the molecule, such as pentaerythritol
Polyhydric alcohol-added polyisocyanates obtained by reacting the above-mentioned compounds, and isocyanate groups of polyisocyanates obtained by reacting the polyisocyanates with blocking agents such as phenols, tertiary alcohols, and secondary amines. A blocked polyisocyanate obtained by blocking is also suitably used as the polyisocyanate compound.

As the epoxy compound, a polyepoxy compound having two or more epoxy groups in the molecule is preferable, and therefore, for example, ethylene glycol, glycerin, sorbitol,
Reaction products of polyhydric alcohols such as pentaerythritol, polyalkylene glycols such as polyethylene glycol, and halogen-containing epoxy compounds such as epichlorohydrin, resorcinol, bis(4-hydroxyphenyl)dimethylethane, phenol/formamide resin, resorcinol. - Reaction products of polyhydric phenols such as formamide resins or phenol resins with halogen-containing epoxy compounds such as epichlorohydrin are preferably used.

The organic solvent used to form the solution of the isocyanate compound or epoxy compound as described above is not particularly limited, but usually, as described above, benzene,
Aromatic hydrocarbons such as xylene and toluene, aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and amyl acetate are preferably used. The solid content concentration in such a solution is not particularly limited, but is usually preferably in the range of 10 to 50% by weight.

The treatment with a solution of an isocyanate compound or an epoxy compound activates the surface of the aromatic polyamide fiber, increases the wettability of the fiber with the resorcinol/formalin resin/halogen-containing polymer latex in the first step, and furthermore, It reacts with the methylol groups of the resorcinol/formalin resin in the first step, or is converted into a resin during vulcanization of the rubber to aromatic polyamide fibers, forming a strong adhesive layer.

The aromatic polyamide fibers treated as described above are then brought into close contact with a rubber compound and vulcanized and bonded under normal processing conditions known for the 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, chlorosulfonated polyethylene, It can be applied to epichlorohydrin rubber, fluororubber, etc. Particularly suitable are natural rubber, styrene-butadiene rubber, chloroprene rubber, and acrylonitrile-butadiene rubber.

Such rubbers may contain appropriate amounts of various reinforcing fillers, anti-aging agents, plasticizers, vulcanization aids, processing aids, etc., which are known as conventional rubber compounds. .

As described above, according to the method of the present invention, in the first step, aromatic polyamide fibers are treated with resorcinol, formalin resin, and halogen-containing polymer latex, and then, in the second step, Aromatic polyamide fibers can be cemented into various rubber formulations by treatment with an adhesive composition containing a methylene acceptor, a methylene donor, and an adhesive rubber that is compatible with the adhered rubber polymer in the rubber formulation. Can be vulcanized and bonded.

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 described below with reference to Examples, but the present invention is not limited to these Examples in any way.

The rubber and latex used in the examples and their preparation will be explained below.

Polyvinyl chloride latex (PVC latex) Zeon manufactured by Nippon Zeon ■ 150X50, solid content 48 layers, polyvinyl chloride chlorine content 57% by weight, s
p value 9.7° Chlorinated rubber latex 30 parts of chlorinated rubber CR-150 manufactured by Asahi Denka Kiku, which has a chlorine content of 65% by weight and an sp value of 9.5, was added to 60 parts of toluene to prepare a mixture, and this was mixed with water. A latex was obtained by adding 100 parts of the mixture and 1.4 parts of an emulsifier (Aerosol 0TR) to water and mixing for 5 minutes using a homomixer. Solid content 20% by weight.

Chloroprene rubber latex Chloroprene rubber latex manufactured by Denki Kagaku Kogyo LV-6
0, solid content 50% by weight, chlorine content of chloroprene rubber 4
1% by weight, sp value 9.2゜Chlorosulfonated polyethylene latex manufactured by Iron Seikagaku Kogyo ■, solid content 40%, solid content 40%, chlorine content of chlorosulfonated polyethylene 25 heavy wall amount, sp value 9.1゜Natural rubber latex solid content 60% by weight, sp value of natural rubber 8.3゜Acrylonitrile/butadiene rubber and tolyl rubber) Nitrile rubber N1pol 1043, manufactured by Nippon Zeon■
Neoprene WRT, manufactured by Showa Denko Co., Ltd., a chloroprene rubber with a p value of 9.7°, and PAP I, manufactured by Upjohn N, an isocyanate compound, with an SP value of 9.2°, were used.

Epoxy compound Denacol EX313 (glycerol polyglycidyl ether) manufactured by Nagase Chemical Industries, Ltd. Chlorinated natural rubber CR-150 manufactured by Asahi Denka 90, Chlorine stand 3165% by weight, s
p value: 9.5° In addition, the peeling state of the obtained adhesive 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 Technora, 1
500D/lX3) was immersed in a treatment solution (al) 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, the samples were immersed in the treatment liquid fb) and then heat-treated at 200° C. for 2 minutes.

After adhering each of the fiber cords treated as described above to a sheet made of unvulcanized rubber compound 1 below,
The adhesive was obtained by vulcanization at 0° C. for 30 minutes.

Rosulfur rubber composition 1 Natural rubber 100 parts Zinc white
5 parts stearic acid
Part 2 Sulfur
2. δ part FEF carbon black
45 parts process oil
5 parts N-oxydiethylene-2-penzthiazylsulfconinamide 1 part 2.
2,4-trimethyl-1,2-dihydroquinoline
0.2 parts The thus obtained adhesive was measured for 180° peel adhesion 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 solutions (al) having the compositions shown in Table 2.
Heat treated at 00°C for 2 minutes, and then the formulation A of Table 1 above.
After immersing in the treatment solution (g) described in 2.
Heat treated for minutes.

Each of the fiber cords treated as described above was brought into close contact with a sheet of the unvulcanized rubber compound 1, and then vulcanized at 50°C for 30 minutes to obtain an adhesive.

Table 1 Regarding this adhesive, the peeling speed was 100n using a peeling tester.
The 180° peel adhesion between the fiber cord and the rubber was measured at 1/min. The results are shown in Table 2.

Furthermore, based on the results of the treatments using the above formulations A and 2 as examples according to the present invention and the treatments using the above formulations E, F, and G as comparative examples, it was determined that the halogen-containing polymer in the treatment liquid (a) FIG. 1 shows the relationship between the halogen content and the adhesive strength of the obtained adhesive. After the aromatic polyamide fibers are treated with RFL containing polyvinyl chloride latex or chlorinated rubber latex, they are 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 solutions (al) having the compositions shown in Table 3, then heat treated at 200°C for 2 minutes, and then treated with the compositions shown in Table 3. After being immersed in the treatment liquid (b) containing the same, heat treatment was performed at 200° C. for 2 minutes.

Each of the fiber cords treated as described above was mixed with the unvulcanized rubber compound 1, unvulcanized rubber compound 2 and 3 shown below.
After adhering to each of the sheets consisting of the following, it was vulcanized at 150° C. for 30 minutes to obtain an adhesive.

Unvulcanized Rubber Compound 2 Neorene WR 7100 parts Magnesium oxide 4 parts Zinc oxide 5 parts SRF carbon black 40 parts 2-mercaptoimidacillin 0.5 parts N, N'-di-β-naphthyl-
p-phenylenediamine 0.5 parts 2.2.4-) dimethyl-1,2-dihydroquinoline 0.5 parts Process oil
10 parts stearic acid
0.5 parts Sulfur rubber 3 parts Nitrile rubber 100 parts Zinc white No. 1 5 parts Stearic acid
1 part sulfur
0.5 part SRF carbon black
40 parts tetramethylthiuram disulfide
2 parts mercaptobenzothiazole 0.5 parts This adhesive was measured for 180° peel adhesion between the fiber cord and the rubber using a peel tester at a peel rate of 100 min/min. The results are shown in Table 3.

In addition, the SP value of the adhered rubber in the rubber compound and the difference between the aromatic polyamide fiber and the adhered rubber in the obtained adhesive when an adhesive composition containing natural rubber or nitrile rubber as the adhesive rubber is used. Figure 2 shows the relationship between the adhesive force and the adhesive force.

Aromatic polyamide fibers are treated with the above-mentioned example formulation A using an adhesive composition containing natural rubber (SP value 8.3). Provides strong adhesion.

Similarly, the adhered rubber is chloroprene rubber (SP value 9°2)
Even when the SP value of chloroprene rubber is close to that of natural rubber, and the difference therebetween is 0.9, strong adhesion can be obtained between the fibers and the chloroprene rubber.

However, when the adhered rubber is nitrile rubber (SP value 9.7), the difference in SP value from the natural rubber contained in the adhesive rubber is as large as 1.4, so the difference between the fiber and the nitrile rubber is large. Strong adhesion cannot be obtained between them.

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 SP value will be the same as that of nitrile rubber. Because of the large difference in , it is not possible to obtain strong adhesion between the fiber 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.

Table 3 Table 3 (Continued) Example 4 The same aromatic polyamide fiber cord as in Example 1 was immersed in the treatment solution (a) of formulation A having the composition shown in Table 1, and then heat treated at 200°C for 2 minutes. Then, a treatment liquid (b) obtained by adding a predetermined amount of chlorinated natural rubber to natural rubber.
After being immersed in water, 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.

This adhesive was tested at a peeling speed of 100 m using a peel tester.
The 180° peel adhesion between the fiber cord and the rubber was measured at m/min. The results are shown in Figure 3. 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 5 The same aromatic polyamide fiber cord as in Example 1 was immersed in a pretreatment solution (C1) having the composition shown in Table 5, and then treated with 200%
℃ for 2 minutes, and then treated in the same manner as in Formulation A in Example 1 above to prepare a treatment solution! 8) and (b), respectively, 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.

This adhesive was tested at a peeling speed of 100 m using a peel tester.
18o between the fiber cord and the rubber at m/min.

Peel adhesion was measured. The results are shown in Table 5.

Table 5 is a graph showing the relationship between content and adhesive strength between aromatic polyamide fibers and natural rubber. Graph showing changes in adhesive force between polyamide fiber and adhered rubber,
FIG. 3 is a graph showing that the blending of chlorinated natural rubber in the adhesive composition has no effect on the adhesive force between the aromatic polyamide fiber and the adhered rubber.

[Brief explanation of the drawing]

Figure 1 shows the amount of chlorine in the chlorine-containing polymer in the resorcinol/formalin resin/chlorine-containing polymer latex. SPI & 10.0 of Glaze Asahi Column

Claims (4)

[Claims] (1) In the method of bonding aromatic polyamide fibers and rubber compounds, aromatic polyamide fibers are bonded to (a) resorcinol/formalin resin and halogen content 45
a first step of treating with a resorcinol/formalin resin/halogen-containing polymer latex containing at least % by weight of a halogen-containing polymer latex; and (b) a methylene acceptor, a methylene donor, and the adhered rubber 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 an adhesive rubber that is compatible with the polymer. (2) Adhesive rubber has +1 solubility parameter of adhered rubber
．． The method of bonding aromatic polyamide fibers and rubber compounds according to claim 1, characterized in that the solubility parameter is in the range of 0 to -1.0. (3) The method for adhering aromatic polyamide fibers and a rubber compound according to claim 1, wherein the adhesive composition contains chlorinated natural rubber. (4) The method for 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.