JP2001064620A - Adhesive composition for rubber and fiber, cord for reinforcing rubber and production of the cord - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive composition for rubber and fiber exhibiting adhesivity to the rubber even in a reduced amount of the adhesive adhered on the fiber, and a cord for reinforcing rubber which holds the characteristic properties of the fiber, which can exhibit a cord property excellent in flexibility, and which has improved adhesivity, that is, excellent adhesive strength drawing power) and excellent adhesion to the rubber on peeling, and improved fatigue resistance, and to provide a method for manufacturing the cord. SOLUTION: This adhesive composition for rubber and fiber is obtained by compounding an adhesive matrix component with silicic anhydride. The first treating liquid containing the adhesive composition for rubber and fiber is imparted to twisted fibers, and the fibers are heat-treated. Subsequently, the second treating liquid containing a mixture (RLF) of an early condensate of resorcin and formaldehyde, and a rubber latex is imparted to the treated fibers, and the fibers are subjected to a heat-treatment to obtain the objective cords for rubber reinforcement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber / fiber adhesive composition, a rubber reinforcing cord, and a method for producing the same. More specifically, an adhesive composition for rubber and fibers effective for improving the adhesion between rubber and fibers, and a rubber reinforcement having improved adhesion to rubber by being treated with this adhesive composition. The present invention relates to a cord for use and a method for manufacturing the same.

[0002]

2. Description of the Related Art As reinforcing agents for rubber structures such as tires, belts and hoses, polyesters represented by polyethylene terephthalate fibers are used because of their superior strength, modulus and dimensional stability compared to other fibers. Fibers such as fibers and aromatic polyamide fibers are used.

However, fibers such as polyester fibers and aromatic polyamide fibers are aliphatic polyamide fibers,
Compared with other fibers such as rayon fiber and polyvinyl alcohol fiber, the adhesiveness to rubber is poor, so that an epoxy compound, an isocyanate compound, a halogenated phenol compound, etc. Various methods have been proposed for the purpose of improving the adhesion to rubber by coating the surface of the fiber.

[0004] For example, typical adhesive treatment agents for polyester fibers include halogenated phenols such as 2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4-chlorophenol and resorcinol-formaldehyde. The reaction product was treated with a liquid (RF) comprising an initial condensate of resorcinol-formaldehyde and rubber latex.
L) (JP-B-46-12551)
Is mentioned. However, when this bonding agent is used, it is necessary to considerably increase the adhesion of the bonding agent to the polyester fiber and to perform a high-temperature heat treatment in order to obtain a sufficient adhesive force (pulling force). By adopting such severe processing conditions, the initial adhesive strength (pull-out force) is satisfied, but there is a problem in that the rubber sticking of the fiber ply peeling is reduced.

As a method for applying an adhesive agent to polyester fibers in a two-bath system, a first treatment liquid containing a mixture of an epoxy compound / blocked isocyanate compound / bentonite as a main active ingredient was applied and heat-treated. After that, a method (JP-B-57-29586) has been proposed in which a second treatment liquid in which an ethylene urea compound is added is added to a mixture (RFL) of a resorcinol-formaldehyde precondensate and a rubber latex, followed by heat treatment. I have.

However, in the above method, the bentonite contained in the first treatment liquid not only has a high true specific gravity, but also has a low viscosity due to its large particle size, and the bentonite is settled. Has a problem in that the quality of the treated fiber varies.

Further, a first treating solution containing a mixture of an epoxy compound, a blocked isocyanate and a rubber latex as a main active ingredient is applied, heat-treated, and then a mixture of a resorcinol-formaldehyde initial condensate and a rubber latex (RFL). ) To which a second treatment liquid containing an ethylene urea compound is added and subjected to a heat treatment (Japanese Patent Publication No. Sho 60-2).
No. 4226) has also been proposed.

However, the above-mentioned method has the advantage that the treated fiber obtained has a relatively high adhesive force (pull-out force) to rubber and increases the amount of rubber with which the ply peels off, but the treated cord becomes hard and the cord becomes harder. Not only the strength is reduced, but also the molding process becomes difficult, and furthermore, the fatigue resistance of the cord treated with the adhesive is reduced.

Further, as a technique for improving the adhesiveness to an aromatic polyamide fiber, for example, JP-A-2-202569
As described in Japanese Patent Application Laid-Open Publication No. H07-157, an aromatic polyamide fiber material is immersed in a first treatment liquid comprising an epoxy compound having two or more epoxy groups in a molecule, and then heat-treated, and then resorcinol-formaldehyde rubber latex There is a method of performing heat treatment after immersion in the (RFL) second treatment liquid.

[0010] Also, Japanese Patent Application Laid-Open No. 3-40875 discloses that
Aromatic polyamide fiber is immersed in the first treatment liquid of a mixed liquid consisting of polyepoxy compound, blocked isocyanate compound and rubber latex, and then heat-treated. Then, special chlorophenol compound is added to resorcinol-formaldehyde rubber latex (RFL). There is also known a method of performing a heat treatment after dipping in a second processing solution.

However, the method described in JP-A-2-202569 cannot provide a satisfactory adhesive force with rubber.

Further, in the method described in JP-A-3-40875, the adhesive strength between the obtained aromatic polyamide fiber and rubber is close to that of polyester fiber, but it is necessary to satisfy the adhesive strength. In addition, there has been a problem that it is necessary to increase the adhesion amount of the adhesive and the cost of the adhesive increases.

[0013]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of study for solving the above-mentioned problems in the prior art. Accordingly, an object of the present invention is to provide a rubber / fiber adhesive composition which exhibits excellent adhesiveness to rubber even when the amount of adhesive attached to fibers such as polyester fibers and aromatic polyamide fibers is reduced. In addition, while maintaining the original properties of the fiber, the fiber exhibits excellent flexibility, and has improved adhesiveness to the fiber, specifically, improved adhesion (pulling force) and rubberized peel adhesion. Another object of the present invention is to provide a rubber reinforcing cord having improved fatigue resistance and a method for manufacturing the same.

[0014]

In order to solve the above-mentioned problems, the rubber / fiber adhesive composition of the present invention mainly has the following constitution. That is, a rubber characterized by comprising silicic anhydride added to the adhesive matrix component.
It is an adhesive composition for fibers.

In the rubber / fiber adhesive composition of the present invention, the following conditions (1) to (5) are preferable conditions, and by obtaining these conditions, it is possible to expect to obtain a better effect. . (1) The silicic anhydride is present in a colloidal state in the adhesive matrix. (2) The amount of the silicic anhydride added to 100 parts by weight of the adhesive matrix component is 1
(3) the particle size of the silicic anhydride is 50 nm or less, (4) the adhesive matrix component is a polyepoxide compound, rubber latex,
A blocked polyisocyanate compound and / or an ethylene urea compound as a main active ingredient, (5) a rubber latex in the adhesive matrix component,
(A) 50-60% by weight of a conjugated diene monomer, (B) 10-20% by weight of a vinylpyridine monomer, and (C)
A terpolymer rubber latex composed of 25 to 35% by weight of a styrene monomer and having a Mooney viscosity of 90 to 120.

The rubber reinforcing cord of the present invention mainly has the following configuration. That is, a rubber reinforcing cord obtained by applying a rubber / fiber adhesive composition to a synthetic fiber, wherein silica anhydride is blended in the rubber / fiber adhesive composition. It is a code for use.

In the rubber reinforcing cord of the present invention, the above-mentioned conditions (2) to (5) and the following condition (6) are preferable conditions, and it is expected that a better effect can be obtained by applying these conditions. Can be. (6) The synthetic fibers are polyester fibers or aromatic polyamide fibers.

Further, the method for producing a rubber reinforcing cord according to the present invention mainly has the following configuration. That is, the synthetic fiber is twisted, a first treatment liquid containing the rubber / fiber adhesive composition is applied thereto, and after heat treatment, a mixture (RFL) of a resorcinol / formaldehyde initial condensate and rubber latex is applied. A method for producing a rubber reinforcing cord, which is applied as a second treatment liquid containing the composition and heat-treated.

In the method for producing a rubber reinforcing cord of the present invention, the following conditions (1) to (4) are preferable conditions,
By applying these conditions, a better effect can be expected to be obtained. (1) As the second treatment liquid, a mixture of resorcinol-formaldehyde precondensate and rubber latex (RF
(L) using an adhesive composition further containing a blocked polyisocyanate compound and / or an ethylene urea compound; (2) a mixture of a resorcinol-formaldehyde precondensate and a rubber latex as the second treatment liquid (RFL) is further co-condensed with parachlorophenol / resorcin / formaldehyde, and an adhesive composition containing a reaction product represented by the following structural formula is used:

[0020]

Embedded image (3) The amount of solids attached to the fibers of the first processing liquid is 0.5 to 3.0% by weight, and the amount of solids attached to the fibers of the second processing liquid is 0.5 to 3.0% by weight. To do,
(4) The synthetic fibers are polyester fibers or aromatic polyamide fibers.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The adhesive composition for rubber and fiber of the present invention is characterized in that silicic anhydride is blended with an adhesive matrix component, and is mainly used as a first treatment liquid in a two-bath treatment method. (2) The addition of silicic anhydride to the treatment liquid is not excluded.

In the rubber / fiber adhesive composition of the present invention, the silicic anhydride is preferably present in a colloidal state.

When this silicic anhydride is mixed and used in the adhesive composition, it is present in a colloidal state, whereby the viscosity stability of the adhesive composition solution is improved, and the adhesive matrix component can be uniformly attached to the fiber surface. The effect is obtained. And, by uniformly adhering the adhesive composition to the synthetic fiber, even if the amount of the adhesive adhering to the fiber is reduced, it is possible to exhibit excellent adhesiveness with rubber, and furthermore, it is flexible and has fatigue resistance. It is possible to realize excellent high-grade rubber reinforcing fibers.

The effect of the colloidal solution of silicic anhydride is to form SiO ₂ on the surface of the fiber, and the silicic acid (SiO ₂ )
Through, the polyepoxide compound, the isocyanate compound and the rubber latex, which are the matrix active ingredients of the adhesive composition, form a hydrogen bond with the polar group of the rubber material, so that a strong adhesive force between the fiber and the rubber is obtained. It is interpreted as being exerted.

The silica anhydride used in the present invention preferably has a particle size of 50 nm or less. Particle size of silicic anhydride is 50n
By setting it to m or less, the dispersibility of the adhesive composition in the solution is improved, the adhesion of the adhesive composition to the fibers becomes uniform, and the effect of improving the adhesiveness to rubber is further exhibited.

In order for silicic anhydride to be present in the adhesive composition for rubber and fiber fibers in a colloidal state, a silicic anhydride may be prepared by adding a colloidal solution with ion-exchanged water or alkaline water.

The adhesive matrix component in the rubber / fiber adhesive composition of the present invention comprises a polyepoxide compound,
Rubber latex, blocked polyisocyanate compound and / or ethylene urea compound are the main active ingredients.

The amount of the silicic anhydride added to the adhesive matrix component is 100 parts by weight of the mixture of the above-mentioned main active ingredients, a polyepoxy compound, a rubber latex, a blocked polyisocyanate compound and / or an ethylene urea compound. It is preferable to add 1 to 13 parts by weight, more preferably 3 to 10 parts by weight, of silicic anhydride with respect to the solid content).

With the optimum addition amount of the silicic anhydride, the rubber-reinforcing cord treated with the adhesive is excellent in the initial adhesive strength, while the fatigue resistance is improved.

The polyepoxide compound in the adhesive matrix component includes a reaction product of a polyhydric alcohol such as pentaerythritol, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol with a halogen-containing epoxide such as epichlorohydrin. , Resorcinol, bis (4-hydroxyphenyl) dimethylmethane,
Bis- (3,4-), a reaction product of a polyhydric phenol such as a phenol-formaldehyde resin and a resorcin-formaldehyde resin with the halogen-containing epoxide.
And polyepoxide compounds obtained by oxidizing unsaturated bond portions such as epoxy-6-methyl-dicyclohexylmethyl) adipate and 3,4-epoxycyclohexene epoxide.

Among them, preferred are reaction products of polyhydric alcohols and epichlorohydrin (polyglycidyl ether compounds of polyhydric alcohols).

The above-mentioned blocked polyisocyanate compound is a compound in which a blocking agent is released by heating to produce an active isocyanate compound, and specific examples thereof include tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, and hexamethylin diisocyanate. , Polyphenolic compounds such as phenol, cresol and resorcinol, lactams such as ε-caprolactam and valerolactam, oximes such as acetoxime, methyl ethyl ketone oxime and cyclohexane oxime, and blocks such as ethyleneimine Reaction products with the agent.

Among these blocked polyisocyanate compounds, aromatic polyisocyanate compounds blocked with ε-caprolactam and aromatic compounds of diphenylmethane diisocyanate give good results.

The ethylene urea compound is used to open the ethylene imine ring by heating and react to improve the adhesiveness. Representative examples thereof include aromatic and aliphatic isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and triphenylmethane triisocyanate, and reactive products of ethylene imine. Aromatic ethylene urea compounds of diphenylmethane diethylene urea give good results.

The main active ingredients of the adhesive composition include:
One or both of the above-mentioned blocked polyisocyanate compound and ethylene urea compound can be contained.

Specific examples of the rubber latex include styrene-butadiene rubber latex, polybutadiene rubber latex, acrylonitrile-butadiene rubber latex, chloroprene rubber latex, chlorosulfonated polyethylene rubber latex, acrylate rubber latex, and natural rubber. Latex and the like. Among them, (A) the conjugated diene monomer is 50 to
60% by weight, (b) vinylpyridine monomer 10-20
It is preferable to use a terpolymer rubber latex consisting of 25% by weight and (C) 25 to 35% by weight of a styrene monomer and having a Mooney viscosity of 90 to 120.

In the above terpolymer rubber latex, 1,3-butadiene is preferably used as (a) the conjugated diene monomer. When the copolymerization amount of the conjugated diene-based monomer is in the range of 50 to 60% by weight, the obtained treated cord can have excellent initial adhesive strength and the obtained treated cord can also have excellent heat resistant adhesive strength. Also,
As the (b) vinylpyridine-based monomer, 2-vinylpyridine is preferably used. The copolymerization amount of this vinylpyridine monomer is optimally 10 to 20% by weight. When the amount is within such a range, the initial adhesive strength of the treated cord can be maintained high,
The cost does not increase.

Further, (iii) styrene is preferably used as the styrene monomer. When the copolymerization amount of the styrene monomer is in the range of 25 to 35% by weight, the heat resistance of the treated cord can be improved.

When the Mooney viscosity of the terpolymer rubber latex is in the range of 90 to 120,
While the fiber treated with the adhesive has excellent heat-resistant adhesive strength, the initial adhesive strength can also be excellent.

The adhesive composition for a fiber of the present invention having the above-mentioned structure is characterized in that an adhesive matrix containing a polyepoxide compound, a rubber latex, a blocked polyisocyanate compound and / or an ethylene urea compound as a main active ingredient is treated with silicate anhydride. By blending, the stability of the viscosity of the adhesive composition solution is improved, and the adhesive matrix component can be uniformly attached to the surface of the synthetic fiber. It is possible to exhibit adhesiveness to rubber, and to obtain a high-grade rubber reinforcing cord that is flexible and has excellent fatigue resistance.

The rubber reinforcing cord of the present invention is a rubber reinforcing cord obtained by adding a rubber / fiber adhesive composition to a synthetic fiber, wherein silicaic anhydride is contained in the rubber / fiber adhesive composition. It is characterized by being blended.
The adhesive composition for rubber / fiber is as described above, and the fact that silicic anhydride is blended in the adhesive composition for rubber / fiber is also as described above. The silicic anhydride is mainly used in the first treatment liquid of the two-bath treatment method, but as described above, it is not intended to exclude the silicic acid in the second treatment liquid. .

Next, a method for producing the rubber reinforcing cord of the present invention will be described. The method for producing a rubber reinforcing cord of the present invention is usually a twist of a synthetic fiber, with a twist factor represented by the following formula, and in the case of a single twist, a raw cord having a twist of 500 to 18,000. . In addition, in the case of a ply twist in which the first twist is applied after the first twist is applied, usually, the first twist coefficient is 500 to 1800 and the first twist coefficient is 800 to 2300.
As a raw cord, a first treatment liquid containing the rubber / synthetic fiber adhesive composition is applied to the raw cord, and after heat treatment,
It is applied as a second treatment liquid containing a mixture (RFL) of a resorcinol-formaldehyde precondensate and a rubber latex. M = TD1 / ² (where M: twist coefficient, T: twist number (t / 10 cm),
D: Indicates fineness (dtex). )

The first treatment liquid used here is preferably a polyepoxide compound in an amount of 12 to 25 parts by weight, more preferably 15 to 25 parts by weight, based on 100 parts by weight of the solid content of the rubber latex, preferably the terpolymer rubber latex. 20 parts by weight, preferably 25 to 45 parts by weight of a blocked polyisocyanate compound and / or an ethylene urea compound,
Further, it is blended in a proportion of 30 to 40 parts by weight, and preferably 1 to 13 parts by weight, more preferably 3 to 13 parts by weight, of silicic anhydride in the form of a colloidal solution with respect to 100 parts by weight of these matrix components in total. It is prepared by blending at a ratio of 10 to 10 parts by weight.

In the mixing ratio of the first processing liquid described above,
Polyepoxy compound, the blended amount of blocked polyisocyanate compound and / or ethylene urea compound,
When the ratio is in the above range, the initial adhesive strength of the rubber reinforcing cord is excellent.

As described above, when the addition amount of the silicic anhydride is the compounding amount, the rubber reinforcing cord has an excellent initial adhesive strength, while the cord is soft and has an excellent fatigue resistance.

This first processing solution is usually used in a total solid concentration of 2
To 12% by weight, preferably 4 to 8% by weight.
Optimally, it is 3.0% by weight. When the solid content concentration of the first treatment liquid and the amount of adhesion to the synthetic fiber are in such preferable ranges, the adhesion rate to the synthetic fiber does not become excessive, and while the fatigue resistance is excellent, the adhesion between the synthetic fiber and the rubber is improved. It will be excellent in power.

The second treatment liquid used in the present invention basically contains a mixture (RFL) of a resorcinol-formaldehyde precondensate and a rubber latex.

Here, the mixture of the resorcinol-formaldehyde precondensate (RF) and the rubber latex (L) is usually called RFL, and the resorcinol-formalin precondensate is obtained under an alkali catalyst. And / or a novolak-type condensate obtained by reacting resorcin represented by the following general formula with formalin under an acidic catalyst.

[0049]

Embedded image The resorcinol and formalin precondensate were obtained under an alkaline catalyst, and the molar ratio of resorcinol to formalin was 1.00: 0.75 to 1.00: 3.0.
0, preferably 1.00: 1.00 to 1.00: 2.
00 range. When a novolak-type condensate of resorcinol and formalin is used, it is preferable that after dissolving in an aqueous alkaline catalyst solution, formalin is added to make the same mol as the resorcinol-formalin initial condensate.

In order to further improve the adhesive strength with rubber, the above-mentioned RFL contains a mixture of the above-mentioned blocked polyisocyanate compound and / or ethylene urea compound, or para-chlorophenol-resorcin-formaldehyde. It is preferable to use a product obtained by condensation and blending a reaction product represented by the following structural formula.

[0051]

Embedded image The rubber latex blended in the second treatment liquid of the present invention includes, together with the terpolymer rubber latex, other rubber latex, for example, styrene-butadiene rubber latex, polybutadiene rubber latex, acrylonitrile-butadiene rubber. Latex, chloroprene rubber latex, chlorosulfonated polyethylene rubber latex, acrylate rubber latex, natural rubber latex, and the like can be appropriately used in combination.

The compounding ratio of the resorcinol-formalin precondensate to the rubber latex in the second treatment liquid is 1: 3 to 1:12, more preferably 1: 4 to 1: 8 in terms of solids weight ratio.
Is preferably within the range.

When a blocked polyisocyanate compound and / or ethylene urea compound is added to this RFL, the amount of addition is 5 to 2 parts per 100 parts by weight of RFL.
The range is preferably 5 parts by weight, more preferably 10 to 20 parts by weight. When a reaction product of a co-condensate with parachlorophenol / resorcin / formaldehyde is added to this RFL, the amount of addition is 2 parts per 100 parts by weight of RFL.
A range of 0 to 50 parts by weight is preferred.

The amount of the second treatment liquid adhering to the synthetic fibers is as follows:
The optimum dry weight ratio is in the range of 0.5 to 3.0% by weight based on the synthetic fibers. By setting the amount of adhesion in the above range, the effect of improving the adhesion to rubber is large, and an increase in the cost of the treatment liquid can be prevented.

In the method for producing a rubber reinforcing cord according to the present invention, the first treatment liquid is applied to the synthetic fibers, and subsequently dried at a temperature of preferably 70 to 150 ° C.
After heat treatment at 00 to 250 ° C., the second
By applying the treatment liquid and drying and heat-treating it preferably under the same conditions as the first treatment liquid, it is possible to obtain a rubber reinforcing cord having extremely excellent adhesion to rubber.

The method of applying the first processing liquid and the second processing liquid to the synthetic fibers includes contact with a roller,
Alternatively, an arbitrary method such as application by spraying from a nozzle or immersion in a liquid bath can be adopted.

Further, in order to control the solid content of each processing solution to the synthetic fiber, means such as squeezing by a pressing roller, scraping off by a scraper, blowing off by blowing air, and suction may be used.

Further, after the above-mentioned drying and heat treatment, the cord can be slid into contact with the edge to perform a braiding softening treatment for obtaining an arbitrary cord rigidity.

The rubber reinforcing cord of the present invention thus obtained is obtained by adding silicic anhydride to the first treatment liquid,
By using the above terpolymer rubber latex as a rubber latex, the adhesive strength with rubber is superior, and flexibility, cord strength and fatigue resistance are improved, as compared with those treated with a conventional adhesive composition. And can provide a very high-grade rubber-reinforced product in the fields of, for example, automobile tires, conveyor belts, V-belts, and hoses.

Further, according to the method for producing a rubber reinforcing cord of the present invention, a gum-up phenomenon that adheres to a roller or the like at the time of treatment with an adhesive composition is reduced, so that the productivity is excellent and the rubber reinforcing cord can be efficiently used. Can be manufactured.

[0061]

The present invention will be specifically described below with reference to examples. Note that, in the examples specifically described below,
Each measurement value was obtained by the following method. (1) T-initial adhesive strength According to the adhesive strength-A method of JIS L 1017 (1983), a treatment cord is embedded in unvulcanized rubber under the following conditions.
Press vulcanization was performed under pressure at an initial adhesive strength of 150 ° C. for 30 minutes and at a heat resistant adhesive strength of 170 ° C. for 70 minutes. After cooling, the cord was pulled out of the rubber block at a speed of 30 cm / min, and the pulling load was reduced to N / It is displayed in cm. (2) Peeling between the plies (rubber adhesion rate, peeling force): polyester fiber Two-ply adhesive-treated cords are cross-plied (cording density 28 /
Inches) in rubber, 150 ° C under pressure,
Perform press vulcanization for 30 minutes, allow to cool, and cool both plies 10c
The peeling is measured at a tensile speed of m / min. The rubber adhesion rate is a value obtained by observing the cord separated from the rubber with the naked eye, and expressing the portion where the rubber is attached to the cord surface in percentage.
The peeling force is a force required for peeling expressed in N / 2 cm. In addition, the rubber compound used for the above-mentioned adhesion evaluation was used. (3) Parallel peel adhesion (rubber adhesion rate, peel force): Aromatic polyamide fiber 2 ply adhesive-treated cord was converted into parallel ply (cord
Embedded in rubber as press-in density of 28 / inch) and press-vulcanized at 150 ° C for 30 minutes under pressure.
After cooling, both plies are peeled and measured at a pulling speed of 5 cm / min. The rubber adhesion rate is a percentage of the portion where the rubber is adhered to the fiber surface expressed by percentage by observing the cord peeled from the rubber with the naked eye, and the peeling force is the force required for peeling in N / inch. expressed. The rubber compound used for the above-mentioned adhesion evaluation was used. (3) Fatigue resistance (Good Rich method disk fatigue) According to JIS L 1017 (1983), (1) polyester fiber has an elongation of 5% and a compression of 20%, and
After repeatedly giving fatigue at 5 rpm for 48 hours, (2) the aromatic polyamide fiber was 1705 at an elongation of 0% and a compression of 5%.
The percentage of strong residual strength after repeated fatigue for 8 hours at rpm is shown as a percentage. The rubber compound used is the same compound used for the above-mentioned bonding. (4) JIS L 1017 (1983) using cord strong tensilon
Year). (5) Cord stiffness Cut the cord into a straight 2cm into 2cm, and use a Tensilon tensile tester bridge (1cm interval, φ: 0.6m)
m) Place on top and hook bar perpendicular to cord (φ: 0.6
mm) was applied to the center of the cord and lowered (2 cm / min) to determine the maximum stress. (6) Resin adhesion amount It was determined by a gravimetric method according to JIS L 1017 (1983). (7) Gum-Up Phenomenon of the First Treatment Solution (Roller Stain) Scrap adhering to the dry turn roller of the computer processing machine was visually judged, and judged according to the following criteria. ：: No scum is observed. Δ: Partially scum is observed. ×: Many scum is observed.

Table 1 shows the copolymerization ratios and Mooney viscosities of the respective components in the terpolymer rubber latexes A to C of the treatment liquids used in the following Examples and Comparative Examples, and Table 1 shows the details of the silicic anhydride. 2 respectively.

[0063]

[Table 1]

[0064]

[Table 2]

[Examples 1 to 8] Sorbitol polyglycidyl ether was added with water and emulsified by using a homogenizer, and was blocked with ε-caprolactam.
4′-diphenylmethane diisocyanate and vinylpyridine-styrene-butadiene latex (Table 1: rubber latex AB) were each 10% by weight in solid content.
The liquid having a concentration of 5.0% by weight mixed at a ratio of / 22% by weight / 68% by weight was mixed with the silicic anhydride shown in Table 2 at a ratio shown in Table 3 to obtain a first liquid.
A treatment liquid was prepared.

Further, resorcinol 1 was added in the presence of caustic soda.
The formalin is reacted with the RF initial condensate (RF-1) and the novolak condensate of resorcinol and formalin obtained by reacting 1.50 mol of formalin with respect to 1 mol of formalin in the same manner as described above. Vinyl pyridine-styrene-butadiene latex (Table 1: rubber latex C) was mixed with the obtained RF initial condensate (RF-2) at a ratio of RF initial condensate / rubber latex = 1/7 (solid content ratio). The mixture was aged at 25 ° C. for 24 hours, and 10 parts by weight of an aqueous dispersion of diphenylmethane-bis 4,4′-N, N′-diethylene urea was added to 100 parts by weight of this RFL to obtain a solid content. A second treatment liquid having a concentration of 10% was obtained.

On the other hand, the melt-spun and drawn yarn has a yarn viscosity of 0.95.
1670 dtex, two filaments of 360 filament polyester fiber, 40 times of lower twist / 10 cm, 40 times of upper twist / 1
A raw cord was obtained by twisting with a twist number of 0 cm.

Similarly, the aromatic fineness of the aromatic polyamide fiber is 1
Two multifilaments of an aromatic polyamide yarn having a filament number of 670 dtex and 1,000 filaments (manufactured by DuPont: Kevlar) were twisted 35 times / 10 cm and twisted 35 times / 1.
A raw cord was obtained by twisting with a twist number of 0 cm.

Next, the first treatment liquid was applied to the raw cord using a computer drip single dipping machine (manufactured by Ritzler, Inc.), and the air wiper pressure was set to polyester cord: 0.15 kg / cm ² ,
Aromatic polyamide: drained under the condition of 0.05 kg / cm ² , dried at 120 ° C. for 100 seconds, and subsequently heat-treated at 240 ° C. for 45 seconds.

Next, the second treatment liquid was applied, and the air wiper pressure was adjusted to polyester cord: 0.30 kg / cm.
^2. Drain the solution under the conditions of 0.10 kg / cm ²
It was dried at 0 ° C. for 100 seconds and subsequently heat-treated at 240 ° C. for 60 seconds.

The solid content of the obtained cord treated with the adhesive was 1.2% by weight of polyester cord and 2.0% by weight of aromatic polyamide cord in the first bath treatment liquid. The solid content of the second treatment liquid was 1.0% by weight of polyester cord and 2.0% by weight of aromatic polyamide cord.
Table 3 shows the characteristic evaluation results of the respective rubber reinforcing cords thus obtained.

[0072]

[Table 3]

[Examples 9 to 14] The same polyester cord and aromatic polyamide cord as those in Examples 1 to 8 were treated with the same first treatment liquid as in Examples 1 to 8 under the same conditions.
The same RFL10 as in Examples 1 to 8 was used as the second bath treatment liquid.
0 parts by weight of parachlorophenol / resorcinol /
Reaction product of co-condensate with formaldehyde (trade name:
(Casabond E, manufactured by Thomas Swan, solid content: 20%)
The mixture was treated under the same conditions as in Examples 1 to 8 by using a mixture obtained by adding 30 parts by weight to a mixed solution having a solid content of 10% by weight. Table 4 shows the characteristic evaluation results of the respective rubber reinforcing cords thus obtained.

[0074]

[Table 4]

[Comparative Examples 1 to 4] In Example 1, copolymer rubber latex having a low Mooney viscosity (shown as rubber latex C in Table 1) was used, and no colloidal solution of silicic anhydride was used. A rubber reinforcing cord was obtained under the same processing conditions as in Example 1. Table 5 shows the characteristic evaluation results of the rubber reinforcing cords thus obtained.

[0076]

[Table 5]

Comparative Example 5 To 333.5 parts by weight of water, 1.3 parts by weight of sodium hydroxide, 16.6 parts by weight of resorcinol and 14.6 parts by weight of 37% formalin were added.
For 2 hours to give an RF resin, which was added to 247 parts by weight of a 40.5% rubber latex C shown in Table 1 above, aged at 25 ° C. for 24 hours, and then parachlorophenol resorcinol. By mixing with 200 parts by weight of a reaction product of a cocondensate with formaldehyde (trade name: Casabond E, manufactured by Thomas Swan Co., Ltd., solid content: 20% by weight), a first treatment liquid having a concentration of 20% by weight is prepared. did.

Next, the first treatment liquid was applied to the same polyester raw cord as in the above example using a computer drip single dipping machine (manufactured by Ritzler, USA), and the air wiper pressure was 0.30 kg / c.
performs a liquid cut under the conditions of m ^2, continue to 100 at 100 ℃
Dried at 245 ° C. for 60 seconds.

The adhesion amount of the above-mentioned one-bath treatment liquid to the fiber was 5.5% by weight. Table 5 also shows the characteristic evaluation results of the thus obtained rubber reinforcing cords.

[0080]

As described above, the adhesive composition for rubber and fiber of the present invention comprises an adhesive matrix containing a polyepoxide compound, a blocked polyisocyanate compound and / or an ethylene urea compound and a rubber latex as main active ingredients. On the other hand, by blending the colloidal solution of silicic anhydride, the stability of the viscosity of the adhesive composition solution is improved, and the adhesive matrix component can be uniformly attached to the fiber surface. It is possible to exhibit excellent adhesiveness to rubber even if the amount is reduced, and to obtain a high-grade rubber reinforcing cord that is flexible and has excellent fatigue resistance.

Further, the rubber reinforcing cord of the present invention has a first
By adding a colloidal solution of silicic anhydride to the treatment liquid and using the above terpolymer rubber latex as the rubber latex, the initial adhesive strength with rubber is lower than that of the conventional adhesive composition. It has excellent heat-resistant adhesive strength and eliminates the gum-up phenomenon that adheres to rollers etc. during treatment with the adhesive composition, thereby improving productivity and improving flexibility, cord strength and fatigue resistance. For example, in the fields of automobile tires, conveyor belts, V-belts and hoses, it is possible to provide extremely high-grade rubber-reinforced products.

Further, according to the method for manufacturing a rubber reinforcing cord of the present invention, the gum-up phenomenon is reduced, the productivity is excellent, and the rubber reinforcing cord can be manufactured efficiently.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09J 161/12 C09J 161/12 161/14 161/14 163/00 163/00 175/04 175/04 D02G 3/48 D02G 3/48 D06M 15/693 D06M 15/693 // D06M 101: 32 101: 34 F term (reference) 4J040 CA001 CA002 CA081 CA082 EB061 EB062 EB071 EB072 EC031 EC032 EC071 EC072 EC261 EC262 EF151 EF152 EF331 EF331 EF331 EF331 EF331 EF331 JB02 KA03 KA16 LA01 LA06 MA10 MA12 MB02 NA05 NA16 PA04 PA09 PA12 PA13 4L033 AA07 AA08 AB01 AC11 BA13 CA34 CA49 CA50 CA68 DA06 4L036 MA05 MA06 PA26 RA24 UA08

Claims (17)

[Claims] 1. An adhesive composition for rubber and fibers, comprising silica anhydride mixed with an adhesive matrix component. 2. The method according to claim 1, wherein said silicic anhydride is present in a colloidal state in an adhesive matrix.
The adhesive composition for rubber and fiber according to the above. 3. The rubber / fiber adhesive composition according to claim 1, wherein the amount of the silicic anhydride is 1 to 13 parts by weight based on 100 parts by weight of the adhesive matrix component. 4. The rubber / fiber adhesive composition according to claim 1, wherein the particle size of the silicic anhydride is 50 nm or less. 5. The adhesive matrix component according to claim 1, wherein the main active ingredient is a polyepoxide compound, a rubber latex, a blocked polyisocyanate compound and / or an ethylene urea compound. Adhesive composition for rubber and fiber. 6. The rubber latex in the adhesive matrix component comprises (a) 50 to 60% by weight of a conjugated diene-based monomer, (b) 10 to 20% by weight of a vinylpyridine-based monomer,
And (c) a terpolymer rubber latex comprising 25 to 35% by weight of a styrene-based monomer and having a Mooney viscosity of 90 to 120.
6. The adhesive composition for rubber and fiber according to any one of items 5 to 5. 7. A rubber reinforcing cord obtained by applying the rubber / fiber adhesive composition to synthetic fibers, wherein silicic anhydride is blended in the rubber / fiber adhesive composition. Cord for rubber reinforcement. 8. The rubber reinforcing cord according to claim 7, wherein the silica anhydride has a particle diameter of 50 nm or less. 9. The rubber reinforcing cord according to claim 7, wherein the addition amount of the silicic anhydride is 1 to 13 parts by weight based on 100 parts by weight of the adhesive matrix component. 10. The adhesive matrix component according to claim 7, wherein the main active ingredient is a polyepoxide compound, a rubber latex, a blocked polyisocyanate compound and / or an ethylene urea compound. Rubber reinforcement cord. 11. A rubber latex in an adhesive matrix component comprising: (a) 50 to 60% by weight of a conjugated diene-based monomer, (b) 10 to 20% by weight of a vinylpyridine-based monomer,
And (c) a terpolymer rubber latex comprising 25 to 35% by weight of a styrene monomer and having a Mooney viscosity of 90 to 120.
The rubber reinforcing cord according to any one of claims 10 to 10. 12. The synthetic fiber according to claim 7, wherein the synthetic fiber is a polyester fiber or an aromatic polyamide fiber.
12. The cord for reinforcing rubber according to any one of 11. 13. A synthetic fiber is twisted, and a first treatment liquid containing the rubber / fiber adhesive composition according to any one of claims 1 to 6 is applied to the twisted synthetic fiber.
A method for producing a rubber reinforcing cord, comprising applying as a second treatment liquid containing a mixture (RFL) of a formaldehyde precondensate and a rubber latex, followed by heat treatment. 14. The method according to claim 1, wherein the second processing liquid is resorcinol.
The rubber reinforcement according to claim 13, wherein an adhesive composition obtained by further mixing a blocked polyisocyanate compound and / or an ethylene urea compound with a mixture (RFL) of a formaldehyde precondensate and a rubber latex is used. Method for manufacturing cords. 15. The resorcinol solution as the second treatment liquid.
An adhesive composition obtained by co-condensing parachlorophenol / resorcinol / formaldehyde to a mixture (RFL) of a formaldehyde precondensate and a rubber latex and blending a reaction product represented by the following structural formula is used. The method for producing a rubber reinforcing cord according to claim 13 or 14, wherein: Embedded image 16. The solid content of the first processing liquid on synthetic fibers is 0.5 to 3.0% by weight, and the solid content of the second processing liquid on synthetic fibers is 0.5 to 3.0% by weight. The method for producing a rubber reinforcing cord according to any one of claims 13 to 15, wherein the content is 0% by weight. 17. The synthetic fiber according to claim 13, wherein the synthetic fiber is a polyester fiber or an aromatic polyamide fiber.
17. The method for producing a rubber reinforcing cord according to any one of items 16 to 16.