JPH02170830A - Bonding of aromatic polyamide fiber and rubber compound - Google Patents

Abstract

PURPOSE:To bond an aromatic polyamide fiber and a rubber compound with remarkably improved bonding strength by treating the aromatic polyamide fiber with a specific latex and then with a specific adhesive composition. CONSTITUTION:An aromatic polyamide fiber is bonded to a rubber compound by treating the fiber with (A) a latex of a resorcinol-formaldehyde resin and a halogen-containing polymer containing (i) a resorcinol-formaldehyde resin and (ii) a halogen-containing polymer latex having a halogen content of >=45wt.% and then with (B) an adhesive composition containing (iii) 10-90wt.% of an isocyanate compound or an epoxy compound and (iv) 90-10wt.% of a bonding rubber compatible to an adherend rubber polymer in the rubber compound. The solubility parameter difference between the adherend rubber and the bonding rubber is preferably +1.0--1.0.

Description

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

Conventional ■Limb Strain 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 of using so-called resorcinol-formalin resin-rubber latex (hereinafter referred to as RFL) as an adhesive is widely known, and according to this method, a certain degree of adhesive strength can be achieved even between synthetic fibers and rubber compounds. can be obtained.

However, the adhesion performance between the reinforcing fiber material and rubber is an important factor that influences the performance of rubber products as described above. The adhesive strength provided 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 No. 49-96048 proposes a method of using RFL made by mixing chlorohydrin rubber latex and chloroprene rubber latex with resorcinol/formalin resin in bonding polyamide fibers and chloroprene rubber. ing.

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 nitrile rubber, ethylene/propylene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, hychlorohydrin rubber, fluororubber, etc. Alternatively, completely saturated rubbers have come to be used in various fields, and such special rubbers are more difficult to adhere to synthetic fibers.

Therefore, regarding the adhesion between such rubber and fibers, Japanese Patent Application Laid-Open No. 61-207442 discloses, for example, when adhering 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 made 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.

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

The present invention for making a dish stand is a method of bonding aromatic polyamide fibers and a rubber compound, in which aromatic polyamide fibers are bonded to (a) a resorcinol/formalin resin and a halogen-containing polymer 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 latex; It is characterized by including a second step of treating with an adhesive composition containing 90 to 10% by weight of an adhesive rubber that is compatible with the rubber polymer in the product.

In the method of the present invention, the resorcinol/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. 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 , and copolymers with chlorobrene 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 and a halogen-containing polymer latex having a halogen content of 45% or more as described above. Aromatic polyamide fibers are treated with halogen-containing polymer latex.

In such a resorcinol/formalin resin/halogen-containing polymer latex, the halogen-containing polymer has high polarity,
It has a high affinity for aromatic polyamide fibers, and not only has excellent wettability, but also forms an adhesive layer with high cohesive force between the 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. 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 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, and is usually 100 to 270°C.
You can process it 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. Additionally, as the halogen content in the halogen-containing polymer increases, the adhesive layer tends to become harder. , 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, in the second step, 10 to 90% by weight of an isocyanate compound or an epoxy compound is added.
and 90 to 10% by weight of an adhesive rubber that is compatible with the adherent rubber polymer in the rubber compound, and by darning treatment, resorcinol, formalin, fir fat, and halogen-containing Even if the amount of polymer latex attached to the aromatic polyamide fiber is small, there will be no variation in adhesive strength between the aromatic polyamide fiber and the adhered rubber, and there will be no reduction in the bending fatigue resistance of the aromatic polyamide fiber.
Moreover, strong adhesion can be achieved.

The above-mentioned isocyanate compound is not particularly limited, but for example, tolylene diisocyanate,
Polyisocyanates such as 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 are also produced by reacting blocking agents such as alcohols and secondary amines to block the isocyanate groups of polyisocyanates.
It is suitably used as a 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 isocyanate compound and the epoxy compound are converted into a resin during the vulcanization of the rubber to the aromatic polyamide fiber, increasing the cohesive force of the adhesive layer formed, and reacting with the methylol groups, etc. of the resorcinol/formalin resin in the first step. and forms a strong adhesive layer.

The adherend rubber having compatibility with the adherend rubber is -m
In general, unvulcanized rubber that is the same as the adhered rubber or similar in terms of chemical structure is used, but even if unvulcanized rubber has a different chemical structure, the bonding rubber If the polarity, 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. By blending it into an adherend rubber compound, it can be used as an adhesive rubber in an adhesive composition.

Although various methods are known for determining the SP value, the SP value is usually determined by the Small method. This method is described, for example, in J. Palnt Technol, 4.
2+ 76 (1970); New Values o
f the 5olability Parameter
rs from Vapor Pressure Da
It is described in ta.

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 adhesive composition contains 10 to 90% by weight of the isocyanate compound or epoxy compound.
The rubber composition contains 90 to 10% by weight of adhesive rubber that is compatible with the rubber polymer in the rubber compound. When the isocyanate compound or epoxy compound and the adhesive rubber are out of 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 wave-type adhesive composition prepared 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 adhesive. 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 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.
The treatment may be carried out for several minutes at a temperature of 0.degree. C. or lower.

According to the present invention, when the adhesive composition uses a rubber that does not contain chloride, such as natural rubber, styrene-butadiene rubber, or acrylonitrile-butadiene rubber, in addition to these adhesive rubbers, Preferably, it contains natural rubber. 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 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 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.

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 to 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 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 hydrochlorohydrin 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 firmly vulcanized into various rubber compounds by treating them with an adhesive composition containing an isocyanate compound or epoxy compound and an adhesive rubber that is compatible with the rubber polymer in the rubber compound. Can be glued.

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.

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

Polyvinyl chloride latex (PVC latex) Zeon manufactured by Nippon Zeo 7fll 150 x 50
, solid content 48% by weight, polyvinyl chloride chlorine content 57% by weight, SP value 9.7° Chlorinated rubber latex chlorine level 165% by weight, SP value 9.5 Chlorinated rubber CR-150 30 manufactured by Asahi Denka ■ A mixture was prepared by adding 1 part to 60 parts of toluene, and this was added to water mixed with 100 parts of water and 1.4 parts of emulsifier (Aerosol 0TR), and mixed for 5 minutes in a homo mixer to obtain latex. . Solid content 2
0% by weight.

Chloroprene rubber latex Rolobrene rubber latex LV-6 manufactured by Denki Kagaku Kogyo ■
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% by weight, chlorine content of chlorosulfonated polyethylene 25% by weight, 5P (tf9.
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, S manufactured by Nippon Zeon ■
P value 9.7° Chloroprene rubber Neoprene WRT manufactured by Showa Denko ■, SP value 9.2° Isocyanate compound As the isocyanate compound, Nippon Polyurethane Kogyo Q grade Millionate MR (polymethylene polyphenyl polyisocyanate) or Kasei Upjohn ■ P.A.P.
I was used.

Epoxy compound Denacol EX313 (glycerol polyglycidyl ether) manufactured by Nagase Chemical Industry ■ Chlorinated natural rubber CR-150 manufactured by Asahi Denka ■, chlorine content 65% by weight, SP value 9.5° Also, in the obtained adhesive, the peeling state was Indicated by:

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 (Technora manufactured by Kijin ■, 1
500D/1X3) 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, the samples were immersed in a treatment liquid (etc.) 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,
A bond was obtained by vulcanization at 0°C for 30 minutes.

N stone〒Rubber 1 part Natural rubber 100 parts Zinc white
5 parts stearic acid
Part 2 Sulfur
2.5 parts FEF carbon black
45 parts process oil
5 parts N-oxydiethylene-2-bendithiazylsulfenamide 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 liquids (a) having the compositions shown in Table 2.
Heat treated at 00°C for 2 minutes, then immersed in the treatment solution described in Formulation A in Table 1 above, and then heated at 200°C.
The sample was heat-treated 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.

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 Table 2.

Table 3 Also, based on the results of the treatments with the above formulations A and the above formulations as examples according to the present invention, and the treatments with the above formulations E, F and G as comparative examples, halogen-containing in the treatment liquid (a) FIG. 1 shows the relationship between the halogen content of the polymer and the adhesive strength of the resulting 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 t8) having the composition shown in Table 3, and then heat treated at 200°C for 2 minutes, and then treated with the composition shown in Table 3. After being immersed in a treatment solution (g) containing
Heat treated for 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 sheet consisting of 150”
C. for 30 minutes to obtain an adhesive.

■Sulfur rubber 8 2 Neorene WRT 100 parts Magnesium oxide 4 parts Zinc oxide
5 parts SRF carbon black 40 parts 2-mercaptoimidacillin
0.5 part N,N'-di-β-naphthyl-p-phenylenediamine 0.5 part 2.2
．． 4-trimethyl-1,2-dihydroquinoline
0.5 part process oil
10 parts stearic acid
0.5 parts ■ Sulfur rubber 4 people 3 Nitrile rubber 100 parts Zinc white No. 1 5 parts Stearin M
l 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 mm/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.

If aromatic polyamide fibers are treated with the above-mentioned Example Formulation A using an adhesive composition containing natural rubber (SP value 8.3), when the adhered rubber is natural rubber, the bond between the fibers and natural rubber will be reduced. Provides strong adhesion.

Similarly, the adhered rubber is chloroprene rubber with a C3P value of 9°2).
Even when this is the case, the SP value of chloroprene rubber is close to that of natural rubber, and the difference therebetween is 0.9, so strong adhesion can be obtained between the fibers and the chloroprene rubber.

Table 3 (continued) 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 1.4, which is large. Therefore, strong adhesion cannot be obtained between the fibers 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 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. A strong adhesion can be obtained.

Example 4 After immersing the same aromatic polyamide fiber cord as in Example 1 in the treatment solution (a) having the composition shown in Table 4,
The sample was heat-treated at 200°C for 2 minutes, then immersed in a treatment solution 0)) having the composition shown in Table 4, and then 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 Table 4.

Table 4 also shows that aromatic polyamide fibers were treated in the same manner as above, except that the weight ratio of the adhesive rubber to the isocyanate compound or epoxy compound in the treatment solution (b) was changed. It was vulcanized and bonded to a sheet made of sulfur rubber compound I.

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 immersed in a treatment solution (a) of formulation A having the composition shown in Table 1, heat treated at 200°C for 2 minutes, and then treated with natural rubber. A treatment solution (b) is prepared by adding a predetermined amount of chlorinated natural rubber.
) and then 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 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
It was heat-treated at 200°C for 2 minutes, then immersed in treatment solutions (a) and (c) in the same manner as in Formulation A in Example 1, 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.
The 180° peel adhesion between the fiber cord and the rubber was measured at m/min. The results are shown in Table 5.

A graph showing changes in adhesive force between the aromatic polyamide fiber and the adhered rubber shown in Table 5, and FIG. 3 shows the weight ratio of adhesive rubber/isocyanate compound or epoxy compound in the adhesive composition and the aromatic polyamide Figure 4, a graph showing the relationship between the adhesive force between fibers and adhered rubber, shows the influence of the blending of chlorinated natural rubber in the adhesive composition on the adhesive force between aromatic polyamide fibers and adhered rubber. This is a graph showing.

[Brief explanation of the drawing]

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 fiber and natural rubber. Adhesive rubber and adhesive rubber with various SP values were used. Figure 1. Figure 2 (excluding weight). figure

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) isocyanate compound or epoxy compound 10-
It is characterized by including a second step of treating with an adhesive composition containing 90 to 10% by weight of an adhesive rubber that is compatible with the adhered rubber polymer in the rubber compound relative to 90% by weight. A method of adhering aromatic polyamide fibers and rubber compounds. (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.