JP2001164233A - Adhesive composition for rubber with fiber, rubber- reinforcing synthetic fiber and fiber-reinforced rubber structural material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive for a rubber with fiber, having a high dispersion stability and a good adhesive property even by using a small applied amount, a synthetic fiber for reinforcing the rubber capable of maintaining the original characteristics of the synthetic fiber and a high adhesive property, and a fiber-reinforced rubber structural material reinforced by using the above synthetic fiber. SOLUTION: This adhesive composition is characterized by blending the adhesive matrix component with fine particles of silisic acid salt compound containing silicon, aluminum and magnesium as main constituting elements, having 1/(0.1-1.0) molar ratio of silicon/aluminum, 1/(0.01-0.1) molar ratio of silicon/magnesium, 10/(1-4) molar ratio of aluminum/magnesium and >=5 wt.% aluminum content, and being adsorbed with a polymer having an ionic functional group.

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 for improving the adhesion between rubber and synthetic fibers, and to the treatment with this adhesive composition, the adhesion to rubber is improved. The present invention relates to a rubber-reinforced synthetic fiber and a fiber-reinforced rubber structure using the rubber-reinforced synthetic fiber.

[0002]

2. Description of the Related Art Polyester fiber represented by polyethylene terephthalate fiber, nylon 6 fiber and nylon 6
Synthetic fibers such as polyamide fibers, aromatic polyamide fibers, and polyvinyl alcohol fibers represented by six fibers have excellent physical properties such as high strength and high Young's modulus. Widely used as reinforcing fibers for rubber structures such as belts and the like. However, as compared with natural fibers, these synthetic fibers have insufficient adhesion to a rubber matrix, and thus various adhesion treatment methods have been proposed. In particular, a one-bath treatment method in which a treatment solution containing a resorcinol-formalin-rubber latex (RFL) adhesive, which is a long-known rubber / fiber adhesive, as a main component, is treated in one stage, or
In the first step, the epoxy compound, isocyanate compound, halogenated phenol compound, etc. are treated in advance with the first treatment liquid containing the adhesive matrix component, and in the second step, the second treatment liquid is treated with the RFL adhesive as a main component. Do 2
Bath treatment methods are widely applied to synthetic fibers.

[0003] For example, as a one-bath treatment method for polyester fibers, there is a one-bath treatment method in which a blocked isocyanate compound and an aromatic polyepoxy compound are added to an RFL adhesive (JP-A-10-46475). )
Etc. are known. In the two-bath treatment method, the fibers are treated with a first treatment liquid containing an aliphatic epoxy compound and a blocked isocyanate compound in the first step to impart adhesiveness, and then the RFL adhesive is added in the second step to the second step. A two-bath treatment method (JP-A-54-73994) for treating as a treatment liquid is known. On the other hand, as a prescription for improving adhesion to polyamide fibers, a one-bath treatment method for specifying the ratio of vinylpyridine to the total weight of vinylpyridine / styrene / butadiene copolymer latex in a rubber latex in an RFL adhesive (JP-A-1-174628) Is known. Further, as a formulation for improving the adhesion to the aromatic polyamide fiber, for example, a first treatment solution comprising a polyepoxy compound, a blocked isocyanate compound and a rubber latex, and then a special chlorophenol compound mixed with an RFL adhesive. A two-bath treatment method such as a method of treating with a two-treatment solution (JP-A-3-40875) is known.

However, in either case, the adhesive composition penetrates not only to the cord surface but also to the inside of the cord, so that the adhesive composition restrains the fiber single yarn inside the cord, and the cord is not squeezed. There has been a problem that it becomes hard and causes a decrease in cord strength and a decrease in fatigue resistance. Also,
Since the adhesive treatment liquid permeates into the inside, unless the adhesion amount (SPU) of the adhesive composition to the synthetic fiber is increased, the adhesive composition cannot uniformly cover the fiber cord. And the cost increases.

[0005] Therefore, an attempt has been made to increase the amount of the coated adhesive treatment agent on the fiber cord surface by preventing the adhesive treatment liquid from penetrating into the interior of the fiber, and to reduce the amount of adhesion of the adhesive treatment agent to the synthetic fiber as a whole. It has been done. For example, a method in which polyester fibers are first treated with a first treatment liquid containing an epoxy compound, a blocked isocyanate compound and a clay which is a silicate compound, and then treated with a second treatment liquid mainly composed of an RFL adhesive (particularly). Kosho 57-
No. 29586) is known. However, in this method, the thickening effect of clay, which is a silicate compound, is sometimes insufficient, and the dispersion stability of the clay in the adhesive is poor, so that sufficient effects cannot be obtained. There was a problem. Furthermore, in order to improve the dispersion stability of the solution, a silicate compound having a high dispersion stability is artificially synthesized instead of a natural silicate compound, and is used as an adhesive composition for rubber and synthetic fibers. Compounding method (Japanese Patent Laid-Open No. 8-10
No. 0165) is also known, but has a problem that the cost is high.

[0006]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a low-cost rubber which has a high adhesive dispersion stability, a good adhesive property even when the amount of adhesive applied is small, and a low cost. -To provide an adhesive composition for fibers. A second object of the present invention is to provide a synthetic fiber for rubber reinforcement that maintains the original properties of the synthetic fiber itself together with adhesiveness even during processing or use in rubber. A third object of the present invention is to provide a fiber reinforced rubber structure reinforced with synthetic fibers.

[0007]

The adhesive composition for achieving the first object of the present invention comprises a composition comprising "silicon, aluminum and magnesium as main constituent elements and a silicon / aluminum molar ratio of 1 / ( 0.1-1.0), and the molar ratio of silicon / magnesium is 1 / (0.01-0.
1) The aluminum / magnesium molar ratio is 10 /
(1-4) and a silicate compound fine particle having an aluminum content of 5% by weight or more and having a polymer having an ionic functional group adsorbed on the surface thereof is blended in an adhesive matrix component. An adhesive composition for rubber and fiber. ".

A rubber reinforcing synthetic fiber which achieves the second object of the present invention is characterized in that the surface of the synthetic fiber is coated with the above-mentioned rubber / fiber reinforcing adhesive composition.

A fiber-reinforced rubber structure which achieves a third object of the present invention is characterized in that a rubber structure is reinforced by using the above-mentioned synthetic fiber for rubber reinforcement.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION First, the rubber / fiber adhesive composition of the present invention will be described. The silicate compound fine particles blended in the adhesive matrix component of the present invention include silicon, aluminum, and magnesium as main constituent elements, and have a silicon / aluminum molar ratio of 1 / (0.1 to 0.1).
1.0), and the silicon / magnesium molar ratio is 1 / (0.
01 to 0.1), an inorganic compound having an aluminum / magnesium molar ratio of 10 / (1 to 4) and an aluminum content of 5% by weight or more. Further, it is desirable to contain at least one selected from sodium, potassium and calcium as a counter ion. Particularly, a natural silicate compound represented by bentonite is inexpensive and easily available. Therefore, purified bentonite that is separated by swelling and that suppresses precipitation of a dispersion is preferably used.

The rubber / fiber adhesive composition of the present invention is characterized in that a polymer having an ionic functional group adsorbed on the surface of the silicate compound fine particles is mixed with an adhesive matrix component. It is not preferable to use a polymer that does not adsorb the polymer, since the water dispersibility of the agent becomes insufficient.

Examples of the adsorption polymer preferably used include various copolymers of acrylic acid, anionic polymers such as styrene sulfonic acid copolymer, polyarylamine, polyvinylamine, vinylpyridine polymers and copolymers, and copolymers of these acids. Examples thereof include a neutralized product, a polymer that has been ammonium-modified by alkylation, and a cationic polymer such as polyethyleneimine, and an anionic polymer such as a sodium salt of an acrylic acid copolymer is particularly preferable.

The swelling power of the silicate compound fine particles in the present invention is preferably 20 to 50 ml / g. The amount of the silicate compound fine particles is preferably in the range of 0.5 to 15% by weight, particularly 1 to 10% by weight, based on the total solid content of the adhesive matrix component. When the amount of the silicate compound fine particles is less than 0.5% by weight, the effect of suppressing the penetration of the adhesive into the treated fiber cord is reduced, the cord strength is reduced, and the adhesion at the time of the low adhesive amount is reduced. A decrease in the force is observed, and when it exceeds 15% by weight, the adhesion of the fiber-treated cord to rubber tends to decrease.

The silicate compound fine particles are blended together with the adhesive matrix component in a treatment solution of the one-bath treatment method or a first treatment solution of the two-bath treatment method. The one-bath treatment method comprises, among synthetic fibers, polyamide fibers or polyester fibers,
Particularly, it is preferably used for high-strength nylon fiber cords, and the two-bath treatment method is preferably used for polyester fibers and aromatic polyamide fibers which require higher adhesiveness.

In the one-bath treatment method, resorcinol-formalin rubber latex (R) is used together with silicate compound fine particles.
FL) An adhesive is blended into the treatment liquid as a main component of the adhesive matrix component. The RFL adhesive used here is a mixture of a resorcinol-formaldehyde precondensate and a rubber latex generally used for rubber material processing. The resorcinol-formalin precondensate has a molar ratio of resorcinol to formaldehyde of 1 / 0.1 to 1/8,
In particular, it is preferably in the range of 1 / 0.5 to 1/5.
The weight ratio of the resorcinol-formalin precondensate to the rubber latex is preferably in the range of 1: 1 to 1:15, especially 1: 5 to 1:15 (solids weight ratio). At this time, if the compounding ratio of the rubber latex is too high,
The tackiness of the treatment liquid becomes extremely high, and the cohesive force of the adhesive film becomes too low, so that the adhesiveness of the obtained fiber cord tends to be adversely affected. Conversely, if the mixing ratio of the rubber latex is too low, the resulting synthetic fiber cord tends to be hard, and the strength and fatigue properties are liable to decrease.

The rubber latex used in the treatment liquid includes, for example, natural rubber latex, styrene / butadiene rubber latex, vinylpyridine / styrene / butadiene copolymer latex, acrylonitrile / butadiene rubber latex, chloroprene rubber latex and the like. These are used alone or in combination.

On the other hand, in the two-bath treatment method, a first treatment liquid containing silicate compound fine particles is applied to a synthetic fiber cord and then treated with a second treatment liquid containing an RFL adhesive as a main component. You. The first treatment liquid used in the two-bath treatment method preferably contains a polyepoxide compound and / or a blocked isocyanate compound as an adhesive matrix component together with the silicate compound fine particles. In addition, it is preferable to add a rubber latex because co-vulcanization occurs with the rubber as an adherend and high rubber adhesion is achieved during a peel test.

As the polyepoxide compound, at least two epoxy groups in one molecule are represented by the compound 1k
Compounds containing at least 2 g equivalent per g are preferred. Specifically, reaction products of polyhydric alcohols such as ethylene glycol, glycerol, sorbitol, pentaerythritol, and polyethylene glycol with halogen-containing epoxides such as epichlorohydrin, resorcinol, pis (4-hydroxyphenyl) dimethylmethane, phenol A formaldehyde resin, a reaction product of a polyhydric phenol such as resorcinol-formaldehyde resin and the halogen-containing epoxide, a polyepoxide compound obtained by oxidizing an unsaturated compound with peracetic acid or hydrogen peroxide, etc.
That is, 3,4-epoxycyclohexene epoxide, 3,
Examples thereof include 4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, and bis (3,4-epoxy-6-methyl-cyclohexylmethyl) adipate. Among them, a reaction product of a polyhydric alcohol and epichlorohydrin, that is, a polyglycidyl ether compound of a polyhydric alcohol is particularly preferred because it exhibits excellent performance.

Similarly, the above-mentioned blocked polyisocyanate compound is an addition compound of a polyisocyanate compound and a blocking agent, and releases a blocking component upon heating to produce an active polyisocyanate compound.

As the polyisocyanate compound, for example, polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, and the like, Compounds having two or more, for example, trimethylolpropane, pentaerythritol, etc., are reacted with an isocyanate group (-NCO) and a hydroxyl group (-
OH), and a terminal isocyanate group-containing polyol adduct polyisocyanate. In particular, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenyl isocyanate are preferred because they exhibit excellent performance.

Examples of the blocking agent for the blocked polyisocyanate compound include phenols such as phenol, thiophenol, cresol and resorcinol, aromatic secondary amines such as diphenylamine and xylidine, phthalic imides, caprolactam and valero. Lactams such as lactams, oximes such as acetoxime, methyl ethyl ketone oxime and cyclohexane oxime, and sodium acid sulfite.

Examples of the rubber latex used in the first treatment liquid include natural rubber latex, styrene / butadiene rubber latex, vinylpyridine / styrene / butadiene copolymer latex, acrylonitrile / butadiene rubber latex, and chloroprene. Rubber latex, etc., which are used alone or in combination. Among them, it is preferable to use vinylpyridine / styrene / butadiene copolymer latex alone or in combination. In the case of combined use, particularly excellent performance is exhibited when one third or more of the total latex weight is used.

In addition, when the synthetic fiber used is a polyester fiber, the use of a polymer in which a vinyl chloride component has been copolymerized in the first treatment liquid greatly enhances the affinity for the polyester fiber, thereby improving the initial adhesion. And the toughness of the adhesive film is improved.

The polymer obtained by copolymerizing the vinyl chloride component preferably has a film formation temperature of 240 ° C. or lower, particularly 180 ° C. or lower. The polymer in which the vinyl chloride component is copolymerized is a compound obtained by copolymerizing vinyl chloride alone or in various forms, such as vinyl chloride and vinyl acetate, vinyl chloride and vinylidene chloride, vinyl chloride and acrylonitrile, and vinyl chloride and vinyl acetate. And a terpolymer of vinyl chloride, vinyl acetate and maleic anhydride, or a mixture thereof.

The above-mentioned components, such as the polyepoxide compound, the blocked isocyanate compound, and the polymer obtained by copolymerizing the vinyl chloride component, are usually added to the adhesive composition as an emulsion, an aqueous dispersion, or an aqueous solution. In order to prepare an emulsion or an aqueous dispersion, for example, the compound is dissolved as it is or if necessary in a small amount of a solvent, and then a known emulsifier such as sodium alkylbenzene sulfonate, sodium salt of dioctyl sulfosuccinate, nonylphenol ethylene oxide is used. What is necessary is just to emulsify or disperse using an addition material etc.

When the adhesive matrix component in the present invention is used as an aqueous dispersion, an appropriate amount of a dispersant, that is, a surfactant, is 0 to 15 wt.
%, Preferably 10 wt% or less, and if it exceeds the above range, the adhesiveness tends to decrease. The addition of a surface tension reducing agent such as an alkylene glycol or a water-soluble silicone is also effective, and the addition thereof improves the wettability at the time of processing, thereby improving the performance when treated at a low concentration.

The second treatment liquid applied to the synthetic fibers after the first treatment liquid in the two-bath treatment method is preferably a mixture of an RFL adhesive and a blocked isocyanate compound. The RFL adhesive has a molar ratio of resorcinol to formaldehyde of 1 / 0.1 to 1/8, preferably 1 / 0.5.
To 1/5, more preferably 1/1 to 1/4. The compounding ratio of the resorcinol-formalin initial condensate and the rubber latex varies depending on the addition ratio of the blocked polyisocyanate compound, but the former: the latter is 1: 1 to 1:15, particularly 1: 3 to 1 in terms of solids weight ratio. 1:12
Is appropriate. The blocked isocyanate compound is the same as that used in the first treatment liquid of the two-bath treatment method,
It is an addition compound of a polyisocyanate compound and a blocking agent. The addition rate of the blocked polyisocyanate compound is preferably 0.5 to 30% by weight based on RFL. The second treatment liquid of this two-bath treatment method has a total solid concentration of 1 to 30.
It is preferred to treat at 5% by weight, especially 5-20% by weight.

Further, particularly when the synthetic fibers are polyester fibers, the second treatment liquid further preferably contains an RFL adhesive, a blocked polyisocyanate compound and / or an aromatic polyepoxide compound, and maintains the adhesiveness when exposed to high temperatures. Rate can be improved. The blocked isocyanate compound is an addition compound of a polyisocyanate compound and a blocking agent similar to that used in the first treatment liquid of the two-bath treatment method.

The aromatic polyepoxide compound is preferably a compound having one or more aromatic rings and two or more epoxy groups in the molecule, and the content of the epoxy group is 2 g equivalent or more per 1 kg of the compound, and particularly preferably 4 to 4 g / kg. More preferably, it is 5 g equivalent. Such aromatic polyepoxide compounds include reaction products of polyhydric phenols and halogen-containing epoxides such as epichlorohydrin, for example, resorcinol, bis (p-hydroxyphenyl) methane,
1,1,2,2-tetrakis (p-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) dimethylmethane, phenol / formaldehyde resin, cresol / formaldehyde resin, resorcin / formaldehyde resin, etc. And an aromatic epoxy resin which is a reaction product of bisphenol A and epichlorohydrin. Among these, glycidyl ethers of phenolic resins represented by the following formula (Formula 1) are particularly preferred.

[0030]

Embedded image

In the formula, X represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 5.

Such an aromatic polyepoxide compound is usually used as an emulsion or dispersion. To prepare an emulsion or dispersion, for example, the aromatic polyepoxide compound as it is or dissolved in a small amount of a solvent as required, and a known emulsifier, for example, sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol What is necessary is just to emulsify or disperse using an ethylene oxide adduct etc.

The weight ratio of the blocked polyisocyanate compound to the aromatic polyepoxide compound is 2: 8 to 9:
1, especially 2: 8 to 6: 4 is preferred. The weight ratio of the total amount of the blocked polyisocyanate and the aromatic polyepoxide compound to the amount of the RFL active component is 4: 6 to 1: 9,
Particularly, a ratio of 5: 5 to 2: 8 is preferable.

Next, the rubber reinforcing synthetic fiber of the present invention will be described. The synthetic fiber for rubber reinforcement referred to in the present invention is a synthetic fiber such as a polyester fiber represented by polyethylene terephthalate fiber, a polyamide fiber represented by nylon 6 fiber or nylon 66 fiber, an aromatic polyamide fiber, and a polyvinyl alcohol fiber. It includes various fiber forms such as yarns, cords, non-woven fabrics, woven and knitted fabrics as raw materials. Particularly, as the polyester fiber generally used, a fiber made of polyester having terephthalic acid or naphthalenedicarboxylic acid as a main acid component and ethylene glycol or tetramethylene glycol as a main glycol component is preferably used. Also,
The denier of the fiber, the number of filaments, the cross-sectional shape, the physical properties of the fiber, the fine structure, the properties of the polymer (concentration of peritoneal group, molecular weight, etc.), the presence or absence of additives in the polymer, and the like are not limited at all.

The treatment solution of the one-bath treatment method of the present invention can be applied to the synthetic fiber by applying the first treatment solution and the second treatment solution of the two-bath treatment method to a synthetic fiber by contact with a roller or spraying from a nozzle or by applying a solution. Means such as immersion in water can be adopted. The solid content of the adhesive composition on the synthetic fiber is preferably in the range of 0.1 to 10% by weight, more preferably in the range of 0.3 to 7% by weight, and more preferably in each treatment solution. Those in the range of 0.5% to 3% by weight are preferred. In order to control the amount of solids adhering to the fiber, in addition to adjusting the concentration and viscosity of the treatment liquid, it is possible to perform the treatment by means of squeezing with a pressing roller, scraping off with a screver, blowing off with air blowing, suction, and beater. In order to increase the amount of adhesion, it may be applied plural times.

According to the present invention, after treating the synthetic fibers with such a treatment liquid, the temperature of each of the treatment liquids is set at 50 ° C. or higher and at 0 ° C. or lower than the melting point of the synthetic fibers. .
Dry and heat treat for 5 to 5.0 minutes. When the fiber used is a polyester fiber, it is more preferable to dry and heat-treat at a temperature of 220 to 250 ° C. for 1 to 3 minutes. If the drying and heat treatment temperatures are too low, adhesion to rubbers tends to be insufficient, while if the temperature is too high, synthetic fibers are melted and fused or markedly reduced in strength, and cannot be put to practical use.

The thus obtained synthetic fiber for reinforcing rubber of the present invention is flexible and resistant to fatigue, has a small amount of the adhesive composition attached, that is, is low in cost, has extremely excellent adhesive strength to rubber, and has a high heat resistance. Is extremely small.

The fiber-reinforced rubber structure in the present invention is:
Specifically, tires, belts, hoses, etc.
The rubber in the rubber structure is reinforced by using the above-mentioned synthetic fiber for rubber reinforcement, and exhibits high-quality characteristics with excellent fatigue resistance, and thus is extremely useful as a fiber-reinforced rubber product.

[0039]

In general, a silicate compound forms various higher-order structures by incorporating various ions into crystals. Therefore, when dispersed in water, a large amount of water is fixed in this structure, and a very large amount of water is fixed in the structure. Shows high viscosity. However, when the ion concentration is high or the surfactant concentration is high, the adsorption of ions and surfactants occurs, the interaction between crystals is suppressed, the viscosity is reduced, and the water dispersion of the agent is increased. Sex becomes unstable. In the present invention, as a means for suppressing such adsorption of ions and surfactants, a polymer having an ionic functional group is adsorbed on the surface of the silicate compound fine particles.

Further, the aqueous dispersion of the silicate compound fine particles of the present invention has an appropriate viscosity, so that the penetration of the adhesive component into the fiber material is suppressed. That is, the rubber / fiber adhesive composition containing the silicate compound fine particles has a large amount present in the fiber material / rubber boundary layer even when the amount of adhesion to the synthetic fiber is small, so that a stable excellent rubber can be obtained. Is obtained. Furthermore, since the adhesive component does not penetrate into the cord, which is a fiber material, the adhesion between the single fibers does not occur, the flexibility of the fiber cord is improved, and the decrease in the fiber cord strength due to the adhesive treatment is effectively prevented. You.

In addition, the addition of the silicate compound fine particles suppresses the aggregation of the adhesive matrix component such as latex and stably exists, so that the adhesive composition uniformly covers the fiber surface. Excellent adhesion to rubber can be obtained even with the amount of adhesion. In addition, the adhesive coating layer has an effect of protecting the synthetic fibers from various chemicals contained in the rubber. However, since the adhesive coating layer is uniformly attached, the protective effect on the synthetic fibers is high. . In particular, polyester fibers are susceptible to amine decomposition and hydrolysis, so that the protective effect is remarkably exhibited. Generally, rubber contains a thiuram-based, sulfenamide-based or guanidine-based vulcanization accelerator, an amine-based antioxidant, and the like.
For example, during the vulcanization process during manufacturing, or during use such as in the case of tires and radiator hoses during high-speed running of automobiles, it promotes the deterioration of synthetic fibers, but when the adhesive composition of the present invention is used In addition, the deterioration of fiber strength and fiber / rubber adhesion is small due to the uniform adhesive coating layer.
Furthermore, since the silicate compound fine particles exhibit stable performance even in the presence of a surfactant, they have a high degree of freedom in adding various additives to the adhesive formulation.

[0042]

The present invention will be described more specifically with reference to the following examples. In addition, each measured value in an Example and a comparative example was calculated | required by the following method.

(1) Peeling Adhesive Strength This shows the adhesive strength between the treated cord and rubber. Seven cords are buried near the surface layer of an unvulcanized rubber sheet containing a carcass containing natural rubber as a main component, and heated at 150 ° C. for 30 minutes for 50 minutes.
kg / cm ² pressing pressure (initial value) or 180
Vulcanized at 50 ° C / cm ² for 20 minutes at a pressing pressure (heat resistance value) of 50 kg / cm ² , and then peeled off five cords at a speed of 200 mm / min in a direction of 90 ° to the rubber sheet surface, leaving the cords at both ends. The force required to perform the operation is indicated by N / 5 lines.

(2) Pull-out adhesive strength This indicates the shear adhesive strength between the treated cord and rubber. Embed the cord in an unvulcanized rubber block containing carcass containing natural rubber as a main component, 150 ° C, 30 minutes, 50k
g / cm ² press pressure (initial value) or 180
At 20 ° C. for 20 minutes at a pressing pressure (heat resistance value) of 50 kg / cm ² , and then the cord was removed from the rubber block by 200 mm.
mm / min, and the force required for extraction is N /
This is indicated by 7 mm.

(3) Swelling power 100 ml of water was put into a measuring cylinder, 2 g of silicate compound fine particles were slowly added thereto, and the mixture was allowed to stand overnight at a constant temperature of 20 ° C., and the gel volume was measured in ml units. 1 g of acid salt
It is converted to per.

(4) Liquid Stability The dispersion state of the first treatment liquid was mixed with the first treatment liquid, and immediately after standing for 1 hour, the state of dispersion was visually observed. did. A: uniform without change in dispersibility. Δ: The dispersion state is non-uniform. X: Precipitation has occurred.

Example 1 A polyepoxide compound, blocked polyisocyanate, rubber latex, PVC latex containing 35 parts of di-2-ethylhexyl phthalate (film formation temperature: 160 ° C.), and an anionic polymer composite purified bentonite (element Composition: Si ₈ (Al _10/3 M
g _2/3 ) O ₂₀ (OH) ₄ Na _2/3 swelling power 50 ml / g
6.0 parts by weight, 20, 20 parts by weight, 44 parts by weight, 30 parts by weight of solid content of Wengel Y200 Co., Ltd.
0.3 parts by weight, and the total solid concentration was adjusted to 10.0 parts by weight.
% By weight. The obtained mixture was used as a first treatment liquid.

An initial condensate having a resorcinol / formalin (R / F) molar ratio of 1 / 0.6 and a solid content of 65% by weight is dissolved under alkaline conditions to obtain a 9% by weight aqueous solution. This is added in an amount of 50 parts by weight to 420 parts by weight of a 9% aqueous emulsion of a vinylpyridine / styrene / butadiene copolymer latex. 3 parts by weight of formalin and 50% by weight
18 parts by weight of a cresol novolak-type aromatic epoxy compound dispersion and 17 parts by weight of a 33% by weight acetoxime blocked diphenylmethane diisocyanate dispersion were added, and a solid content concentration of 20% by weight was aged for 48 hours. did.

A multifilament of 1500 denier / 384 filaments made of polyethylene terephthalate having an intrinsic viscosity of 0.95 is firstly twisted at 40 T / 10 cm, and the two of them are twisted together at 40 T / 10 cm to give a three-ply twist.
A cord of 000 denier / 768 filament was obtained.

This cord was immersed in a first treatment liquid using a contributer treatment machine (tire code treatment machine manufactured by CA Ritzler Co., Ltd.), dried at 130 ° C. for 2 minutes, and subsequently dried at 240 ° C. for 1 minute. Heat treatment for 2 minutes, followed by immersion in the second processing solution, followed by drying at 170 ° C. for 2 minutes,
Subsequently, heat treatment was performed at 240 ° C. for 1 minute. In the obtained treated polyester tire cord, the first treatment liquid had an adhesive solids adhesion amount of 2.0% by weight, and the second treatment liquid had an adhesive solids adhesion amount of 1.5% by weight.

The obtained treated cord was embedded in an unvulcanized rubber containing carcass containing natural rubber as a main component,
The composition was vulcanized at 30 ° C. for 30 minutes and evaluated according to the above method. Table 1 shows the results.

Example 2 Example 1 was used as the second treatment liquid.
Except that the cresol novolak-type aromatic epoxy compound dispersion was not added to the components of the second treatment liquid used in Example 2, the same treatment as in Example 1 was carried out and evaluated. The results are shown in Table 1.

Example 3 Example 1 was used as the first treatment liquid.
No PVC latex is added to the components of the first processing solution used in Step 1, and a cresol novolak-type aromatic epoxy compound dispersion is added to the components of the second processing solution used in Example 1 as the second processing solution. Except for the absence, the same thing as in Example 1 was used and processed and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4 The first processing liquid and the second processing liquid were the same as those used in Example 1, and the first processing liquid had an adhesive solid component adhesion amount of 1.0% by weight, and the second processing liquid The treatment was performed in the same manner as in Example 1 except that the amount of the adhesive solid component attached to the liquid was changed to 1.1% by weight, and the evaluation was performed. The results are shown in Table 1.

Comparative Example 1 Example 4 was used as the first treatment liquid.
Example 4 except that the anionic polymer composite purified bentonite was not added to the components of the first treatment liquid used in Example 4.
Was used and treated and evaluated in the same manner as in Example 4.
The results are shown in Table 1.

Comparative Example 2 Example 4 was used as the first treatment liquid.
Except that the swelling power was changed to an anionic polymer composite purified bentonite having a swelling power of 18 ml / g, the blended component of the first treatment liquid used in the above was changed to 18 ml / g.
Example 4 was used and evaluated in the same manner as in Example 4. The results are shown in Table 1.

Comparative Example 3 Example 4 was used as the first treatment liquid.
Example 4 was used except that the anion-based polymer composite purified bentonite as a component of the first treatment liquid used in Step 1 was changed to bentonite having a swelling power of 48 ml / g, which was not modified with an anionic polymer. The same treatment as in Example 4 was performed and evaluated. The results are shown in Table 1.

Comparative Example 4 Example 4 was used as the first treatment liquid.
Anionic polymer composite purified bentonite as a component of the first treatment liquid used in the above was converted to silicate compound fine particles having a swelling power of 5 ml / g and an ideal chemical composition of Mg ₃ (Si ₄ O ₁₀ ) (OH) _2. Except for the change, the same thing as in Example 4 was used and evaluated in the same manner as in Example 4. The results are shown in Table 1.

[0059]

[Table 1]

[0060]

The adhesive composition for rubber and fiber of the present invention comprises:
Since the dispersion stability is good, the process stability is high, and a large amount of adhesion to synthetic rubber is achieved with a low amount of adhesion to synthetic fibers, so that significant cost reduction is possible. Further, the rubber reinforcing synthetic fiber of the present invention is flexible and resistant to fatigue, has a small amount of the adhesive composition attached, that is, is low in cost, and has an extremely excellent adhesive force to rubber, and can be used in a high-temperature atmosphere in rubber. Even when exposed, a high-quality fiber-reinforced rubber structure can be obtained because the inherent properties and adhesiveness of the synthetic fiber are maintained at a high level. INDUSTRIAL APPLICABILITY The fiber-reinforced rubber structure of the present invention is of high quality having excellent fatigue resistance, and therefore is extremely useful as a tire, a belt, and a hose.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D02G 3/48 D02G 3/48 D06M 11/79 D06M 15/55 15/55 15/693 15/693 101: 32 // D06M 101: 32 11/12 F term (reference) 4J040 CA011 CA041 CA141 DB041 DC031 DC071 DE021 DF081 DG021 DH041 EB061 EC031 EC061 EC071 EC081 EC261 EF141 EF151 EF331 HA316 HA356 JA03 JB02 MA05 LA07 LA12 LA05 AA18 AB01 BA09 BA19 DA21 4L033 AB01 AC11 BA94 CA34 CA49 CA50 CA68 4L036 MA05 PA21 PA26 UA06

Claims (13)

[Claims] 1. A silicon / aluminum molar ratio of 1 / (0.1 to 1.0) and a silicon / magnesium molar ratio of 1 / (0.01 to 0) containing silicon, aluminum and magnesium as main constituent elements. .1) a silicate compound having a molar ratio of aluminum / magnesium of 10 / (1 to 4), an aluminum content of 5% by weight or more, and a polymer having an ionic functional group adsorbed on the surface; An adhesive composition for rubber and fibers, wherein fine particles are blended in an adhesive matrix component. 2. The silicate compound fine particles having a swelling force of 2
The adhesive composition for rubber and fiber according to claim 1, wherein the amount is 0 to 50 ml / g. 3. The rubber / fiber adhesive composition according to claim 1, wherein the silicate compound fine particles contain at least one selected from sodium, potassium and calcium. 4. The rubber / fiber adhesive composition according to claim 1, wherein the silicate compound fine particles are bentonite. 5. The adhesive composition for rubber and fiber according to claim 1, wherein the adhesive matrix component is mainly composed of resorcinol-formalin rubber latex (RFL). . 6. The rubber / fiber adhesive composition according to claim 1, wherein the adhesive matrix component contains a polyepoxide compound and / or a blocked isocyanate compound. 7. The adhesive composition for rubber and fiber according to claim 1, wherein the amount of the silicate compound fine particles added to the adhesive matrix component is 0.5 to 15% by weight. . 8. A synthetic fiber for rubber reinforcement, wherein the synthetic fiber is treated with the adhesive composition according to any one of claims 1 to 7. 9. The synthetic fiber is treated with the adhesive composition according to claim 1 as a first treatment liquid, followed by resorcinol-formalin rubber latex (RFL).
A synthetic fiber for rubber reinforcement, which is treated with a second treatment liquid containing as a main component. 10. The synthetic fiber for reinforcing rubber according to claim 9, wherein the synthetic fiber is a polyester fiber. 11. The synthetic fiber for reinforcing rubber according to claim 10, wherein the first treatment liquid contains a polymer obtained by copolymerizing a vinyl chloride component. 12. The synthetic fiber for reinforcing rubber according to claim 9, wherein the second treatment liquid contains a blocked isocyanate compound and / or an aromatic polyepoxide compound. 13. A fiber-reinforced rubber structure in which the rubber in the rubber structure is reinforced by using the rubber-reinforced synthetic fiber according to claim 8. Description: