JP3266976B2 - Adhesive composition of rubber and fiber and composite of rubber and fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-fiber adhesive composition and a fiber-rubber composite treated with the adhesive composition, and more particularly to a nitrile group-containing highly saturated copolymer. The present invention relates to an adhesive composition used as an adhesive for a composite of a polymer rubber and a fiber, and a composite obtained using the adhesive composition. The adhesive composition of the present invention has excellent adhesive performance between the fiber and the rubber, and can significantly improve the wear resistance of the fiber. It is suitable as an adhesive (fiber treatment agent) in a belt made of fibers.

[0002]

2. Description of the Related Art Composites of rubber and fibers are used in many fields such as belts, rubber hoses and diaphragms. In the field of belts, there are automotive timing belts, poly-ribbed belts, wrapped belts, V-belts, etc.
Usually, it is composed of a composite of a woven base fabric and rubber. For example, in the case of a V-belt, the periphery of the belt is protected by canvas, and in the case of a tooth-shaped belt, a covering cloth is laminated on the teeth.

Conventionally, chloroprene rubber and acrylonitrile-butadiene copolymer rubber, which are oil-resistant rubbers, have been mainly used as rubbers. Higher heat resistance has been required in response to miniaturization and sealing of the engine room for noise control, etc., and recently, nitrile group-containing highly saturated oils having both heat resistance and oil resistance have been recently developed. Polymer rubber has been used (Japanese Patent Publication No. 43767/1990). As fibers, polyamide fibers such as vinylon fiber, polyester fiber, nylon, and aramid (aromatic polyamide), cotton, rayon, and the like are used in the form of staples, filaments, cords, ropes, and woven fabrics such as canvas. I have.

In the case of a timing belt, for example, the teeth are protected by a nylon base cloth, but the adhesion between the rubber and the base cloth is increased, and the wear caused by the engagement between the belt and the gear is suppressed. Therefore, the base fabric is generally treated with a solvent-based rubber paste. However, in recent years,
In order to eliminate environmental pollution due to organic solvents, a treatment technique using a water-based adhesive instead of a treatment using a solvent-based rubber paste is desired.

Conventionally, as an adhesive between a nitrile group-containing highly saturated copolymer rubber and a fiber, an adhesive composition containing a nitrile group-containing highly saturated rubber latex having an iodine value of 120 or less and a resorcinol-formaldehyde resin (Japanese Patent Application Laid-Open (kokai) No. H10-157556). Kaisho 63-
No. 248879), a nitrile group-containing unsaturated copolymer rubber latex obtained by an emulsion polymerization method is treated with hydrogen in the presence of a hydrogenation catalyst to select carbon-carbon double bonds in the copolymer. Adhesive composition containing highly hydrogenated nitrile group-containing highly saturated copolymer rubber latex and resorcinol-formaldehyde resin (JP-A-3-16723)
No. 9) has been proposed. Since these adhesive compositions are water-based, there is no problem of environmental pollution due to organic solvents, and the fibers treated with the adhesive composition have excellent adhesion to nitrile group-containing highly saturated copolymer rubber. ing.

However, according to the research results of the present inventors, the fibers treated with the adhesive composition containing the nitrile group-containing highly saturated copolymer rubber latex and the resorcinol-formaldehyde resin have a solvent-based rubber paste. It was found that the abrasion resistance was not always sufficient as compared with the case of using. In particular, when these adhesive compositions are used as a treating agent for a base fabric for a belt, the abrasion resistance of the belt is not sufficient, and improvement is required.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water-based adhesive composition of rubber and fiber, and to impart sufficient abrasion resistance to the fiber treated with the adhesive composition. It is to provide an adhesive composition that can be used. More specifically, the object of the present invention is to remarkably improve the abrasion resistance of a composite of a nitrile group-containing highly saturated copolymer rubber and a fiber, particularly a belt in which the rubber is combined with a base fabric such as canvas. It is an object of the present invention to provide a water-based adhesive composition which can be improved and a composite using the adhesive composition.

The inventors of the present invention have conducted intensive studies to overcome the problems of the prior art, and as a result, a carboxyl group-containing highly saturated nitrile rubber latex was added to a resorcinol-formaldehyde resin and a Group II metal of the periodic table. Although the composition containing the compound is water-based, it is not only excellent as an adhesive between the nitrile group-containing highly saturated copolymer rubber and the fiber, but also has a high degree of compatibility with the fiber treated with the composition. Have been found to be able to impart abrasion resistance, and based on the knowledge, the present invention has been completed.

[0009]

Thus, according to the present invention, a carboxyl group-containing highly saturated nitrile rubber (A) latex is added to a resorcin-formaldehyde resin (B),
And the adhesive composition of the rubber and fibers, characterized in that by blending the Periodic Table Group II metal compound (C) is provided. Further, according to the present invention, there is provided a rubber-fiber composite comprising a nitrile group-containing highly saturated copolymer rubber (D) having an iodine value of 120 or less and a fiber treated with the adhesive composition. Is done.

Hereinafter, the present invention will be described in detail. (Carboxyl group-containing highly saturated nitrile rubber latex)
The latex of the carboxyl group-containing highly saturated nitrile rubber (A) used in the present invention is a latex of a highly saturated copolymer rubber containing a carboxyl group and a nitrile group.
The carboxyl group-containing highly saturated nitrile rubber (A) is obtained by hydrogenating a conjugated diene unit of an unsaturated nitrile-conjugated diene-ethylenically unsaturated carboxylic acid copolymer,
An unsaturated nitrile-conjugated diene-ethylenically unsaturated carboxylic acid-other ethylenically unsaturated monomer copolymer, or a hydrogenated version of the copolymer may be used.

The carboxyl group-containing highly saturated nitrile rubber (A) used in the present invention needs to be a highly saturated rubber, and when the iodine value is used as an index of saturation, the iodine value (JIA K-0070) is usually used. Is 120 or less, preferably in the range of 0 to 100. If the iodine value is too high, the heat-resistant adhesive strength is undesirably reduced. Such a carboxyl group-containing highly saturated nitrile rubber (A) is preferably obtained by hydrogenating an unsaturated copolymer rubber containing a carboxyl group and a nitrile group.

The carboxyl group-containing highly saturated nitrile rubber (A) latex is prepared by hydrogenating a carboxyl group-containing unsaturated nitrile rubber in a solution state, and then converting the solution into a latex by a phase inversion method (Japanese Patent Application Laid-Open No. 63-63). 248879
Or a latex of a carboxyl group-containing unsaturated nitrile rubber obtained by an emulsion polymerization method in a latex state by a hydrogenation reaction (JP-A-2-178305, JP-A-3-167239).
issue). An unsaturated nitrile-conjugated diene-ethylenically unsaturated carboxylic acid-other ethylenically unsaturated monomer copolymer having a small ratio of conjugated diene units and an iodine value of 120 or less, the copolymer Latex can be used as it is.

The following are examples of monomers used for producing the carboxyl group-containing highly saturated nitrile rubber (A). Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3
-Aliphatic conjugated dienes such as pentadiene and halogen-substituted butadiene. These conjugated dienes may be used alone or in combination of two or more.

The unsaturated nitrile may be any one having a polymerizable unsaturated bond with a nitrile group. Specific examples thereof include α, β-unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile. Can be. As the ethylenically unsaturated carboxylic acid monomer,
For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like can be mentioned.

Other copolymerizable ethylenically unsaturated monomers include, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Trifluoroethyl acrylate, tetrafluoropropyl (meth) acrylate, ethyl itaconate, butyl fumarate, butyl maleate, methoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth)
Esters of unsaturated carboxylic acids such as methoxyethoxyethyl acrylate; such as (meth) acrylamide, N-methylol (meth) acrylamide, N, N'-dimethylol (meth) acrylamide, N-ethoxymethyl (meth) acrylamide N-substituted (meth) acrylamide; cyanomethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 1-cyanopropyl (meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, (meth) A) cyanoalkyl (meth) acrylates such as 3-cyanopropyl acrylate; fluoroalkyl vinyl ethers such as fluoroethyl vinyl ether; vinyl pyridine.

These monomers are usually copolymerized by an emulsion polymerization method. As the method of emulsion polymerization, a conventionally known method may be employed, and any of a batch system, a semi-batch system, and a continuous system may be employed, and the polymerization temperature and pressure are not particularly limited. The emulsifier used in the polymerization is not particularly limited, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used. Among them, an anionic surfactant is preferable. The amount of the emulsifier used is not particularly limited, but from the viewpoint of the adhesive strength of the adhesive composition obtained from this latex, is usually 1 to 10 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of all monomers. Parts. Further, a polymerization initiator, a molecular weight regulator and the like may be those which are usually used.

Copolymers using these monomers include copolymers containing 30 to 90% by weight of conjugated diene units, 10 to 50% by weight of unsaturated nitrile units, and 2 to 10% by weight of ethylenically unsaturated carboxylic acid units. Polymers are preferred. The conjugated diene unit is preferably selectively hydrogenated by hydrogenating the copolymer to obtain a highly saturated copolymer having an iodine value of 120 or less. The use of a polymer rubber is preferred from the viewpoint of satisfying both the initial adhesive strength, heat resistant adhesive strength and water resistant adhesive strength. In addition, the carboxyl group-containing highly saturated nitrile rubber (A) preferably contains a carboxyl group in an amount of 0.02 ephr or more from the viewpoint of improving the adhesion and the abrasion resistance. The content of the carboxyl group is more preferably 0.02 to 0.10 ephr.

Specific examples of such a carboxyl group-containing highly saturated nitrile rubber (A) include butadiene-acrylonitrile- (meth) acrylic acid copolymer rubber and isoprene-butadiene-acrylonitrile- (meth) acrylic acid copolymer. Rubber, isoprene-acrylonitrile-
A rubber obtained by hydrogenating a (meth) acrylic acid copolymer rubber or the like may be used.

(Resorcinol-formaldehyde resin) As the resorcinol-formaldehyde resin (B), known resins (for example, those disclosed in JP-A-55-142635) can be used and are not particularly limited. The reaction ratio between resorcinol and formaldehyde is usually 1: 1 to 1: 5
(Molar ratio), preferably 1: 1 to 1: 3 (molar ratio).

The resorcin-formaldehyde resin is usually 5 to 30 parts by weight, preferably 8 to 20 parts by weight, based on 100 parts by weight of the solid content of the latex of the carboxyl group-containing highly saturated nitrile rubber (A) on a dry weight basis. Used in parts proportions. When this use ratio exceeds 30 parts by weight,
The adhesive layer becomes too hard, and the flexibility is impaired.

Further, in order to enhance the adhesive strength, conventionally used 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or a similar compound, isocyanate, blocked isocyanate, ethylene urea, Polyepoxide, modified polyvinyl chloride resin and the like can be used in combination.

(Compound of Group II Metal of Periodic Table) As the metal of Group II of the periodic table, for example, magnesium (M
g), calcium (Ca), barium (Ba), zinc (Zn), and the like. Examples of the compound (C) of these metals include oxides and hydroxides. Among these, zinc oxide is particularly preferred.

The compound (C) of Group II metal of the periodic table is
1 to 20 parts by weight, based on 100 parts by weight of the solid content of the latex of the carboxyl group-containing highly saturated nitrile rubber (A),
Preferably, it is used in a mixing ratio of 3 to 10 parts by weight. The compound (C) of Group II metal of the periodic table is preferably blended as an aqueous dispersion. By blending the compound (C) of the Group II metal of the periodic table, the abrasion resistance of the fiber treated with the adhesive composition can be significantly improved.

(Adhesive Composition) The adhesive composition of the present invention comprises:
It is obtained by mixing a latex of a carboxyl group-containing highly saturated nitrile rubber (A) with a resorcinol-formaldehyde resin (B) and a compound (C) of a Group II metal of the periodic table. Is usually formulated as an aqueous dispersion. Further, the preferred compounding ratio of each of these components is based on 100 parts by weight (solid content) of the carboxyl group-containing highly saturated nitrile rubber (A).
5 to 30 parts by weight (in terms of dry weight) of formaldehyde resin (B) and compound (C) 1 of Group II metal of the periodic table
20 parts by weight. When these ratios are out of the above ranges, the abrasion resistance of the fiber treated with the adhesive composition is reduced.

The addition of sulfur used in the vulcanization reaction of rubber, a vulcanization accelerator and the like to the adhesive composition of the present invention further improves the abrasion resistance. Further, an aqueous dispersion of carbon black may be added as long as the object of the present invention is not impaired. Further, a part of the latex of the carboxyl group-containing highly saturated nitrile rubber (A) may be used as a styrene-butadiene copolymer rubber latex, a modified latex thereof, and an acrylonitrile-butadiene copolymer rubber as long as the gist of the present invention is not impaired. Latex and its modified latex, chloroprene rubber latex, chlorosulfonated polyethylene latex, natural rubber latex and the like can be used alone or in combination of two or more.

(Treatment of Fiber with Adhesive Composition) Examples of the fiber used in the present invention include vinylon fiber, polyester fiber, polyamide fiber such as nylon and aramid (aromatic polyamide), cotton, rayon and the like. These fibers are used in the form of a woven fabric such as staples, filaments, cords, ropes, and canvas. In particular, in order to obtain a belt having excellent wear resistance, it is preferable to use a woven fabric such as canvas.

Fiber (base fabric) using the adhesive composition of the present invention
Is not particularly limited, and the same method as in the case of using a known resorcin-formalin resin / polymer latex adhesive composition can be employed. An example of the processing method is as follows. First, the fiber
Dipping treatment with the adhesive composition, if necessary, usually 100 ~
After drying at 150 ° C. for about 0.5 to 10 minutes,
Heat treatment. The condition of the heat treatment is not particularly limited, and is a time and a temperature sufficient for reacting and fixing the adhesive composition adhered by immersion, and is usually about 140 to 140.
Performed at 250 ° C. for several minutes. In order to increase the adhesive strength, the fiber may be immersed in an isocyanate solution, an epoxy solution, or a mixture thereof and dried before the immersion treatment in the adhesive composition. The drying temperature in this case is desirably equal to or lower than the drying temperature after dipping the adhesive composition. In the present invention, the adhesion amount of the solid content of the adhesive composition is not particularly limited, but is usually 2 to 20% by weight, preferably 3 to 10% by weight based on the fiber.

(Composite of Rubber and Fiber) As the nitrile group-containing highly saturated copolymer rubber (D) to be composited with the fiber, the above-mentioned JP-B-2-43767 and JP-A-63-248879 are described.
And known ones disclosed in JP-A-3-167239 and the like can be used. The same thing as the carboxyl group-containing highly saturated nitrile rubber (A) used for the latex is also used.

Highly saturated copolymer rubber containing a nitrile group (D)
Examples of hydrogenated butadiene-acrylonitrile copolymer rubber, isoprene-butadiene-acrylonitrile copolymer rubber, isoprene-acrylonitrile copolymer rubber, and the like; butadiene-methyl acrylate-acrylonitrile copolymer rubber, butadiene −
Acrylic acid-acrylonitrile copolymer rubber and the like and hydrogenated rubbers; butadiene-ethylene-acrylonitrile copolymer rubber, butyl acrylate-ethoxyethyl acrylate-vinyl chloroacetate-acrylonitrile copolymer rubber, butyl acrylate-ethoxyethyl An acrylate-vinyl norbornene-acrylonitrile copolymer rubber is exemplified.

These nitrile group-containing highly saturated copolymer rubbers (D) usually contain a nitrile group-containing monomer unit at a ratio of 10 to 60% by weight from the viewpoint of oil resistance, and iodine from the viewpoint of heat resistance. Value is 120 or less, preferably 100
Below, more preferably, it is desirable to be 80 or less.

Nitrile group-containing highly saturated copolymer rubber (D)
Is vulcanized after being compounded with the fiber, but the vulcanizing agent is not particularly limited, and ordinary sulfur vulcanizing agents, peroxide-based vulcanizing agents and the like can be used. To compound the nitrile group-containing highly saturated copolymer rubber (D) with the fiber treated with the adhesive composition of the present invention, specifically, a vulcanizing agent and a filler are added to the rubber (D). After the fiber treated with the adhesive composition is embedded in a rubber compound prepared by adding a compounding agent such as the above, vulcanization is performed. Vulcanization conditions are usually 0.5 to 1
Under a pressure of 0 MPa at 130 to 200 ° C. for 1 to 120 minutes.

[0032]

The present invention will be described more specifically with reference to the following examples. Parts and percentages in Preparation Examples, Examples, and Comparative Examples are on a weight basis unless otherwise specified.

[Preparation Example 1] (Preparation of latex) 240 parts of water, 2.5 parts of sodium alkylbenzenesulfonate, 35 parts of acrylonitrile, 4 parts of methacrylic acid
Parts were placed in this order, and the inside of the bottle was replaced with nitrogen, and then 61 parts of butadiene was press-fitted. 0.25 parts of ammonium persulfate was added as a polymerization initiator, and a polymerization reaction was carried out to obtain a carboxylated acrylonitrile-butadiene copolymer rubber latex.

Next, the solid content of the latex was adjusted to 12
After adjusting to 400% by weight (total solid content 48
g) was charged into a 1-liter autoclave equipped with a stirrer, and nitrogen gas was flowed for 10 minutes to remove dissolved oxygen in the latex. Then, 100 g of palladium acetate was used as a hydrogenation catalyst.
mg was dissolved in 240 ml of acetone and added. After replacing the inside of the system twice with hydrogen gas, hydrogen gas was injected to 30 atm, the contents were heated to 50 ° C., and reacted for 6 hours.
Then, after removing the organic solvent using an evaporator, the organic solvent was concentrated until the solid content concentration became about 40% by weight to obtain a carboxyl group-containing highly saturated nitrile rubber latex (A-1) having an iodine value of 30.

Except that the amount of methacrylic acid was changed, a carboxyl group-containing highly saturated nitrile rubber latex (A-2) having a different carboxyl group content was prepared in the same manner as in the method of preparing the latex (A-1). A-3) was obtained. In addition, except that 35 parts of acrylonitrile and 65 parts of butadiene were used as monomers, a latex (A
An acrylonitrile-butadiene copolymer rubber was obtained in the same manner as in the preparation method 1), and a hydrogenation reaction was similarly performed to obtain a highly saturated nitrile rubber latex (B-1). The carboxyl group content of each latex thus obtained,
Table 1 shows the iodine value, the average particle size, the solid content, and the pH.

[0036]

[Table 1]

Preparation Example 2 (Preparation of Aqueous Dispersion of Zinc Oxide) According to the formulation shown in Table 2, an aqueous dispersion of zinc oxide having a solid content of 50% was prepared using a magnetic ball mill.

[0038]

[Table 2] (* 1) Naphthalene-formalin condensate manufactured by Kao Corporation

[Preparation Example 3] (Preparation of resorcin-formaldehyde resin solution / latex) 6.5 parts of resorcin, formalin (37% concentration)
9.4 parts and 3.0 parts of sodium hydroxide (10% concentration) were dissolved in 139.6 parts of water, and reacted at 25 ° C. for 6 hours with stirring. 250 parts of the latex (40% concentration) obtained in Preparation Example 1, 22.6 parts of aqueous ammonia (14% concentration), and 120.4 parts of water were added to the obtained solution, and 2 parts of the solution were stirred.
The reaction was carried out at 5 ° C. for 20 hours to obtain an adhesive composition.

[0040]

[Table 3]

[Preparation Example 4] (Preparation of rubber compound to be adhered) According to the compounding recipe shown in Table 4, a nitrile group-containing highly saturated copolymer rubber and various compounding agents were kneaded on a roll, and about 2. A 5 mm thick rubber compound sheet was prepared.

[0042]

[Table 4] (* 2) Nitrile group-containing highly saturated copolymer rubber manufactured by Zeon Corporation: iodine value 28, bound acrylonitrile amount 36% (* 3) Nitrile group-containing highly saturated copolymer rubber manufactured by Zeon Corporation: iodine value 4, bonded Acrylonitrile content 36% (* 4) α, α'-bis (t-butylperoxyisopropyl) benzene

[Examples 1 to 3] RFL prepared by blending a resorcinol-formaldehyde resin solution with latex (A-1)
An adhesive composition was prepared by mixing zinc oxide as a water dispersion in the liquid with varying amounts as shown in Table 5. Using the obtained adhesive composition, a base cloth made of nylon 66 was immersed, and then heat-treated at 160 ° C. for 2 minutes.
The nylon base fabric treated with the adhesive composition was superimposed on the rubber compound sheet (a) prepared according to the compounding recipe shown in Table 4 and vulcanized at 150 ° C. for 30 minutes under a pressure of 5 MPa to obtain 15c
An mx 15 cm square composite of nylon base cloth and rubber was obtained.

The abrasion resistance of the nylon base fabric treated with the adhesive composition was evaluated for the obtained composite using a Taber abrasion tester for carpet (manufactured by Toyo Seiki Co., Ltd.). The test conditions were a load of 1 kg, a wear surface temperature of 120 ° C. (irradiation with an infrared lamp), and a disk rotation of 10,000 times.

With respect to the abrasion resistance, the abrasion loss of the treating agent (adhesive composition) was evaluated on a five-point scale according to the following criteria. 5: normal surface of processing agent 4: 25% abrasion of processing agent 3: 50% abrasion of processing agent 2: 75% abrasion of processing agent 1: 90% abrasion of processing agent

Comparative Example 1 A composite was prepared and subjected to an abrasion test in the same manner as in Examples 1 to 3, except that zinc oxide was not blended.

Comparative Example 2 Nitrile Group Content 37% by Weight
Except for using a highly saturated nitrile rubber latex (B-1) having no carboxyl group, a composite was prepared and subjected to an abrasion test in the same manner as in Examples 1 to 3. Table 5 summarizes the measurement results.

[0048]

[Table 5] According to Examples 1 to 3, a nylon base fabric treated with an adhesive composition obtained by mixing a resorcinol-formaldehyde resin and zinc oxide with a highly saturated nitrile rubber latex containing a carboxyl group was subjected to a resistance test using a Taber abrasion tester for carpet. It turns out that it is excellent in abrasion property.

Example 4 A mixture of latex (A-2) and an RFL solution containing a resorcinol-formaldehyde resin solution was mixed with 5 parts of zinc oxide as an aqueous dispersion.
The same operations as in Examples 1 to 3 were performed to produce a composite of a nylon base fabric and rubber, and a wear test was performed.

Example 5 An RFL solution obtained by mixing a resorcinol-formaldehyde resin solution with a latex (A-3) was mixed with 5 parts of zinc oxide as an aqueous dispersion.
The same operations as in Examples 1 to 3 were performed to produce a composite of a nylon base fabric and rubber, and a wear test was performed.

Comparative Example 3 Nitrile Group Content 37% by Weight
The same operation as in Examples 1 to 3 was carried out by blending 5 parts of zinc oxide as an aqueous dispersion with an RFL solution containing a highly saturated nitrile rubber latex (B-1) resorcinol-formaldehyde resin solution having no carboxyl group. Was performed to prepare a composite of a nylon base fabric and rubber, and a wear test was performed. Table 6 shows the results of Examples 3 to 4 and Comparative Example 3.

[0052]

[Table 6]

According to Examples 4 and 5, the carboxyl group was reduced to 0.1.
By using a nylon base fabric treated with an adhesive composition containing a resorcinol-formaldehyde resin and zinc oxide in a carboxyl group-containing highly saturated nitrile rubber latex containing from 02 to 0.10 ephr, the abrasion resistance of the nylon base fabric is It can be seen that this is greatly improved as compared with the case where the adhesive composition was treated with the adhesive composition using a highly saturated nitrile rubber latex having no carboxyl group (Comparative Example 3).

Examples 6 to 8 RFL prepared by blending a resorcinol-formaldehyde resin solution with latex (A-1)
3, 5 and 10 parts of zinc oxide were added to the liquid to prepare three types of adhesive compositions. The nylon base fabric treated with these adhesive compositions was superimposed on a rubber compound sheet (b) prepared according to the compounding formula shown in Table 4, and a press pressure of 5 MPa, 1
The mixture was vulcanized at 60 ° C. for 30 minutes to obtain a composite of 15 cm × 15 cm square fiber and rubber. Further, a wear test was performed in the same manner as in Examples 1 to 3.

Comparative Example 4 A composite was prepared and subjected to a wear test in the same manner as in Examples 6 to 8, except that zinc oxide was not blended.

Comparative Example 5 Nitrile Group Content 37% by Weight
Except for using the high-saturated nitrile rubber latex (B-1) having no carboxyl group, a composite was prepared and subjected to an abrasion test in the same manner as in Examples 6 to 8. Example 6-
Table 8 shows the measurement results of Comparative Example 8 and Comparative Examples 4 and 5.

[0057]

[Table 7] According to Examples 6 to 8, even if the vulcanization system of the rubber to be worn is changed to peroxide, the nylon base fabric treated with the adhesive composition of the present invention has the same abrasion resistance as the sulfur vulcanization system. I understand.

[0058]

The adhesive composition comprising the carboxyl group-containing highly saturated nitrile rubber latex of the present invention and a resorcinol-formaldehyde resin and a compound of a Group II metal for periodicity is mixed with the fiber treated with the adhesive composition. And excellent wear resistance can be imparted. Further, the composite of rubber and fiber of the present invention is particularly suitable as a treatment for a belt base fabric such as a timing belt requiring heat resistance because the base fabric has flexibility even after a long-term heat aging test. is there.

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Claims (2)

(57) [Claims] 1. A rubber comprising a carboxyl group-containing highly saturated nitrile rubber (A) latex, and a resorcin-formaldehyde resin (B) and a compound (C) of a Group II metal of the periodic table. Adhesive composition of fibers and fibers. 2. A rubber / fiber composite comprising a nitrile group-containing highly saturated copolymer rubber (D) and a fiber treated with the adhesive composition according to claim 1.