JP2001234143A - Adhesive treatment agent for rubber/fiber, and fibrous cord for reinforcing rubber and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive treatment agent for rubber/fiber which inhibits the gum up phenomenon in an adhesive treatment agent-imparting step (dipping), improving the operation stability in the step without detriment to properties such as adhesion to rubber or fatigue resistance, and to obtain a rubber- reinforcing fibers prepared by treating with the adhesive treatment agent for rubber/fiber. SOLUTION: This adhesive treatment agent at least contains a rubber latex as a matrix component and sodium lignosulfonate in an amount of 0.5-10 wt.% of the rubber latex.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in an adhesive treatment agent used for a fiber for reinforcing rubber of a fiber / rubber composite product represented by a tire, a belt, a hose and the like. More specifically, the present invention relates to a rubber / fiber adhesive treatment agent having improved operation stability in a treatment agent application step (dipping), a rubber reinforcing fiber cord treated with the rubber / fiber adhesion treatment agent, and a method for producing the same. is there.

[0002]

2. Description of the Related Art Polyamide represented by poly-ε-caprolactam (nylon 6) fiber or polyhexamethylene adipamide (nylon 66) fiber is used as a reinforcing material for fiber-rubber composite products such as tires, belts and hoses. Synthetic fibers such as fibers, polyester fibers represented by polyethylene terephthalate fibers, and aromatic polyamide fibers are generally used.

[0003] Among them, polyester fibers are mainly used because the balance of performance such as strength, modulus, dimensional stability and fatigue resistance is superior to other fibers.

However, synthetic fibers typified by polyester fibers generally have poor adhesion to rubber.
For the purpose of ensuring the adhesiveness between synthetic fibers and rubber, a method of applying an adhesive agent mainly composed of rubber latex to synthetic fibers has conventionally been adopted.

For example, Japanese Patent Publication No. 60-24226 discloses that a synthetic fiber is provided with a first treatment liquid containing a mixture of an epoxy compound, a blocked isocyanate compound and a rubber latex as a main active ingredient, and is subjected to a heat treatment. Further, there is disclosed a method of applying a second treatment liquid in which an ethylene urea compound is added to a mixture (RFL) of a resorcinol-formaldehyde precondensate and a rubber latex, and performing a heat treatment.

However, in this method, the emulsion of the blocked isocyanate compound or the rubber latex contained in the first processing solution is unstable, so that a gum-up phenomenon occurs in the dipping step, and as a result, the productivity is reduced. There was a problem of doing.

[0007] The gum-up phenomenon is a phenomenon in which a single component in the adhesive treatment solution that has deviated from the surfactant adheres to the roller in the heat treatment zone in a lump. In order to alleviate this gum-up phenomenon to some extent, the surface of the roller is cooled by passing water through the inside of the roller, but the improvement effect by this is not perfect.

[0008] When such gum up occurs on the roller surface, the machine must be stopped to remove the lump, which not only complicates the operation and significantly lowers the productivity but also reduces the synthetic fiber. The adhesion state of the adhesive treatment agent becomes non-uniform, and as a result, the adhesiveness to rubber and the quality are also lowered. Therefore, the improvement has been constantly demanded.

As a method of suppressing the gum-up phenomenon without deteriorating performance such as adhesion to rubber, for example,
JP-A-8-60555 discloses that a polyester fiber is treated with a first treating agent containing an epoxy compound, a blocked isocyanate compound and a rubber latex, and then a mixture (RFL) of a resorcinol-formalin precondensate and a rubber latex is prepared. Polyisocyanate compound,
And 0.01 to 0.1 with respect to the total solid content of both.
Although a method of treating with a second treating agent containing 15% by weight of an anionic surfactant has been proposed, it is a reality that even this method has not sufficiently obtained the effect of suppressing the gum-up phenomenon.

[0010]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above. Therefore, the object of the present invention is to
This rubber / fiber adhesive treatment agent improved the operation stability by suppressing the gum-up phenomenon in the adhesion treatment agent application process (dipping) without impairing the performance such as adhesion to rubber and fatigue resistance. It is an object of the present invention to provide a rubber reinforcing fiber treated with a fiber bonding agent and a method for producing the same.

[0011]

In order to solve the above-mentioned problems, the rubber / fiber bonding agent of the present invention mainly has the following constitution. That is, an adhesive treatment agent containing at least a rubber latex in a matrix component, wherein the solid content of the rubber latex is 100 parts by weight and the sodium salt of lignosulfonic acid is contained in an amount of 0.5 to 10 parts by weight. It is a bonding agent for rubber and fiber.

The following conditions (1) and (2) are preferable conditions, and it is expected that a better effect can be obtained by applying these conditions. (1) The matrix component does not contain resorcinol-formaldehyde precondensate; (2) The matrix component is a polyepoxide compound in addition to rubber latex.
At least one compound selected from the group consisting of blocked polyisocyanate compounds and ethylene urea compounds.

Further, the rubber reinforcing fiber cord of the present invention comprises:
It mainly has the following configuration. That is, a rubber reinforcing fiber cord in which the surface of a synthetic fiber cord is provided with a rubber / fiber bonding treatment agent, wherein at least the surface of the fiber cord is coated with an adhesion treatment agent containing a sodium salt of lignosulfonic acid. A fiber cord for rubber reinforcement.

[0014] The following conditions (1) to (5) are preferable conditions, and it is expected that a better effect can be obtained by applying these conditions. (1) The adhesive treatment agent applied to the surface of the synthetic fiber cord comprises an inner layer portion and an outer layer portion, and the matrix component of the adhesive treatment agent in the inner layer portion does not substantially contain a resorcinol-formaldehyde precondensate, and the outer layer portion has The matrix component of the bonding agent contains a resorcinol-formaldehyde precondensate, (2) the bonding agent is a rubber latex,
(3) including at least one selected from the group consisting of a polyepoxide compound, a blocked polyisocyanate compound and an ethylene urea compound as a matrix component;
The bonding agent is 0.8 to 6.0 based on the weight of the fiber cord.
(4) the synthetic fiber cord is made of polyester, and (5) the synthetic fiber cord is a twisted polyester fiber.

Further, the method for producing a fiber cord for rubber reinforcement according to the present invention mainly has the following constitution. That is, a method for producing a rubber reinforcing fiber cord, which comprises applying the adhesive treatment agent according to any one of claims 1 to 3 to the surface of the synthetic fiber cord and then performing a heat treatment. A method for producing a fiber cord for rubber reinforcement characterized by the following.

Incidentally, the following conditions (1) to (3) are preferable conditions, and it is expected that a better effect can be obtained by applying these conditions. (1) A second treatment liquid containing a mixture of resorcinol / formaldehyde precondensate and rubber latex as a matrix component is further applied to the surface of the synthetic fiber cord, followed by heat treatment. (2) Matrix component of the second treatment liquid Is composed of a mixture with a resorcinol-formaldehyde precondensate and a rubber latex, and a blend with a blocked polyisocyanate compound and / or an ethylene urea compound. (3) The synthetic fiber cord is made of polyester.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the details of the rubber / fiber bonding agent of the present invention will be described. The adhesive treatment agent for rubber and fiber of the present invention is characterized in that a sodium salt of lignosulfonic acid having a basic skeleton of phenylpropane represented by the above general formula is added to a matrix component of the adhesion treatment agent. . As described later, the sodium salt of lignosulfonic acid is mainly used in the first bath treatment method.
It is used by blending it with the processing solution.
It does not preclude blending into the processing solution. That is, based on 100 parts by weight of the solid content of the rubber latex contained in the matrix component of the bonding agent, 0.5 to 10 parts by weight of a sodium salt of lignosulfonic acid having a basic skeleton of phenylpropane represented by the above general formula. It is an essential condition to contain.

Further, the adhesive treatment agent for rubber and fiber of the present invention has a more excellent effect because at least the matrix component of the adhesion treatment agent directly in contact with the fiber cord does not substantially contain a resorcinol-formaldehyde precondensate. Can be demonstrated.

Here, the expression "substantially free of resorcinol-formaldehyde precondensate" means that resorcinol-formaldehyde precondensate may be contained in a small amount to the extent that the object of the present invention is not impaired.

Further, when the matrix component contains at least one compound selected from a polyepoxide compound, a blocked polyisocyanate compound and an ethylene urea compound in addition to the rubber latex, a more excellent effect can be exhibited.

That is, an aqueous dispersion of a blocked isocyanate compound, rubber latex, or the like in the adhesive treatment agent is diluted with rubber latex or the like due to being diluted from a stock solution or receiving a mechanical shock. The surfactant contained as a raw material comes off and the stability deteriorates, and the solid polymer from which the surfactant has come off adheres to the roll, causing a gum-up phenomenon.

However, in the rubber / fiber bonding agent of the present invention, the gum-up phenomenon is remarkably improved by the combined use of rubber latex and the above-mentioned sodium salt of lignosulfonic acid.

In the adhesive treatment agent of the present invention, lignosulfonic acid is one in which the bond of the side chain of lignin is cleaved by the action of a chemical solution to introduce a sulfone group. These are combined at one ratio.
This sodium salt of lignosulfonic acid is a polymer compound having a molecular weight of hundreds to millions, and is a polymer electrolyte that dissociates in water. Further, it exhibits a performance as a dispersant due to a surfactant-like structure having a large hydrophobic skeleton of C ₆ -C ₃ and a sulfone group and other hydrophilic groups at the same time. The sodium salt of lignosulfonic acid is produced when pulping wood.

The amount of the sodium salt of lignosulfonic acid in the adhesive treatment agent of the present invention is 0.5 to 10 parts by weight based on 100 parts by weight of the solid content of the rubber latex contained in the matrix component of the adhesive treatment agent. Things. If the amount of the sodium salt of ligninsulfonic acid is less than 0.5 parts by weight, the gum-up phenomenon cannot be effectively suppressed, while if it exceeds 10 parts by weight, sufficient adhesion to rubber is secured. Can not do it.

Specific examples of the rubber latex contained in the matrix component of the adhesive agent of the present invention include natural rubber latex, styrene / butadiene copolymer rubber latex, acrylonitrile / butadiene copolymer rubber latex, chloroprene rubber latex and vinyl Pyridine / styrene / butadiene terpolymer rubber latex and the like can be used alone or as a mixture. However, from the viewpoint of heat resistance and adhesiveness, the rubber latex has a solid content of 100% by weight. A rubber latex in which a vinylpyridine / styrene / butadiene terpolymer rubber latex accounts for 50% by weight or more is preferably used.

Specific examples of epoxy compounds that can be used as the matrix component of the adhesive agent of the present invention include:
Reaction products of polyhydric alcohols such as pentaerythritol, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol with halogen-containing epoxides such as epichlorohydrin, resorcin, bis (4-hydroxyphenyl) dimethylmethane, phenol -Reactive products of polyhydric phenols such as formaldehyde resin and resorcin-formaldehyde resin with the halogen-containing epoxides, bis- (3,4-epoxy-6-methyl-dicyclohexylmethyl) adipate, 3,4-epoxycyclohexene Examples include a polyepoxide compound obtained by oxidizing an unsaturated bond portion such as an epoxide.
Preferably, it is a reaction product of a polyhydric alcohol and epichlorohydrin (a polyglycidyl ether compound of a polyhydric alcohol). Those obtained by dissolving these compounds as they are or by adding a small amount of a wetting agent as needed can be used.

The blocked polyisocyanate compound which can be used as a matrix component of the adhesive agent of the present invention is an addition compound of a polyisocyanate compound and a blocking agent. Isocyanate compound, specifically, tolylene diisocyanate, metaphenylene diisocyanate, diphenyl methane diisocyanate,
Polyisocyanate compounds such as hexamethylin diisocyanate and triphenylmethane triisocyanate; phenols such as phenol, cresol and resorcin; lactams such as ε-caprolactam and valerolactam; acetoxime; methyl ethyl ketone oxime;
Reaction products with oximes such as cyclohexane oxime and blocking agents such as ethyleneimine.

Among these blocked polyisocyanate compounds, good results are obtained particularly when aromatic polyisocyanate compounds blocked with ε-caprolactam and aromatic compounds of diphenylmethane diisocyanate are used.

Further, the ethylene urea compound which can be used as a matrix component of the adhesive treatment agent of the present invention is a compound which, when heated, causes the ethylene imine ring to open 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. Good results are obtained when using an aromatic ethylene urea compound of diphenylmethane diethylene urea.

The matrix component of the adhesive agent of the present invention may contain one or both of the above-mentioned blocked polyisocyanate compound and ethylene urea compound. These are usually used in an aqueous dispersion using a dispersant.

Further, the rubber reinforcing fiber cord of the present invention comprises:
A rubber reinforcing fiber cord to which a rubber / fiber adhesive treatment agent is applied, wherein at least the surface of the fiber cord is coated with the above-described adhesive treatment agent containing a sodium salt of lignosulfonic acid. Is what you do. The reason why the sodium salt of lignosulfonic acid should be blended in the rubber / fiber bonding agent is as described above. The sodium salt of lignosulfonic acid is mainly used by being blended into the first treatment liquid of the two-bath treatment method, but excludes blending of the sodium salt of lignosulfonic acid into the second treatment liquid. This is not the case as described above.

Next, the details of the method for producing the rubber reinforcing fiber cord of the present invention will be described. In the method for producing a fiber cord for rubber reinforcement of the present invention, a fiber obtained by twisting a synthetic fiber is usually used as a raw material fiber cord, but the synthetic fiber can be used without being twisted according to the purpose.

The method for producing a fiber cord for rubber reinforcement according to the present invention has a twist coefficient represented by the following formula when used as a raw fiber cord obtained by twisting a synthetic fiber. It is desirable to use one having a twist coefficient of 600. M = TD1 / ² (where M: twist coefficient, T: number of twists (t / 10 cm), D: fineness (dte
x)).

In the case of a ply twist in which plying is performed after priming is performed, priming and plying are performed. More preferably, the plying twist coefficient represented by the above formula is 1300 to 25.
It is preferable to use a fiber cord having a twist coefficient of 900 to 1800.

A first treatment liquid comprising the above-mentioned rubber / fiber bonding treatment agent is applied to such a raw material fiber cord, and heat-treated to obtain a polyester fiber cord for rubber reinforcement of the present invention. In addition, a mixture of resorcinol-formaldehyde precondensate and rubber latex (R
It is also preferable to apply a second treatment liquid containing FL) and perform heat treatment.

Further, as the matrix component of the second treatment liquid, a mixture of a resorcinol-formaldehyde precondensate and a rubber latex (RFL) and a mixture with a blocked polyisocyanate compound and / or an ethylene urea compound are employed. By doing so, more excellent effects can be exhibited.

By using a synthetic fiber cord made of polyester, the effects of the present invention can be further exhibited.

The heat treatment after the application of the first treatment liquid or the second treatment liquid is usually performed at a temperature of 220 to 260 ° C. and a temperature of 30 to 1 ° C.
It is desirable to perform this for about 20 seconds.

When the adhesive treatment matrix component of the first treatment liquid contains any one or more of a polyepoxide compound, a blocked polyisocyanate compound and an ethylene urea compound, the rubber component also contained in the matrix component The amount of the sodium salt of lignosulfonic acid added to 100 parts by weight of the solid content of the latex was 1
It is preferably in the range of from 6 to 6 parts by weight. By setting the content in this range, the adhesiveness to rubber is the most excellent, and the operation stability in the adhesive treatment treatment step becomes the most preferable.

In the adhesive treatment agent of the first treatment liquid, the total solid concentration including the epoxy compound, the blocked isocyanate compound, the rubber latex (vinyl pyridine / styrene / butadiene terpolymer latex) and the sodium salt of lignosulfonic acid is as follows: , 2 to 15% by weight, and even 3
Preferably, the content is within the range of 8 to 8% by weight, and by setting the content in such a range, operation stability such as reduction of dirt on the machine is desirably improved, and a rubber-reinforced fiber having good adhesion to rubber is obtained. Can be.

On the other hand, the second treatment liquid is a mixture of resorcinol-formalin precondensate and rubber latex (usually RF
L) and a blocked polyisocyanate compound and / or an ethylene urea compound.

The resorcinol-formalin precondensate (R
The molar ratio of resorcinol to formaldehyde in F) is preferably in the range from 1: 0.5 to 1: 5, especially from 1: 1 to 1: 3.

Examples of the rubber latex include vinyl pyridine / styrene / butadiene terpolymer rubber latex,
Styrene butadiene copolymer rubber latex, polybutadiene rubber latex, acrylonitrile butadiene copolymer rubber latex, chloroprene rubber latex, chlorosulfonated polyethylene rubber latex, acrylate rubber latex, natural rubber latex, etc. The rubber latex is preferably used together with the rubber to be adhered.

The mixing ratio of the resorcinol-formalin precondensate (RF) and the rubber latex (L) in the RFL is 1: 2 to 1:12, particularly 1: 4 to 1 in terms of solids weight ratio.
The ratio is preferably in the range of 1: 9. By setting the ratio in such a range, generation of scum can be suppressed, and a fiber cord for rubber reinforcement having good flexibility and adhesiveness can be obtained.

When adding a blocked polyisocyanate compound and / or an ethylene urea compound as an adhesion improver to the RFL, the amount of addition is 3 to 25% by weight, especially 5 to 18% by weight, based on the RFL. It is preferable that the content be in the range. By setting the content in the range, the cost of the adhesive treatment agent can be suppressed, and the rubber reinforcing fiber having high flexibility and good flexibility can be obtained by the treatment.

As a method for adhering the first treatment liquid and the second treatment liquid to the synthetic fiber cord, any method such as immersion, contact with a roller, and application by spraying from a nozzle can be selected. In order to control the amount, using means such as blowing off with air blowing, suction, squeezing with a pressure roller, scraping off with a scraper, etc., the solid adhesion amount of the adhesive treatment agent to the finally obtained synthetic fiber cord is It is preferably 0.5 to 4.0% by weight, more preferably 0.8 to 2.0% by weight in the inner layer part derived from the first treatment liquid, and 0.5 to 4.0% in the outer layer part derived from the second treatment liquid. % By weight, and even 0.8 to 1.5% by weight
It is preferable to be within the range.

In the method for producing a rubber reinforcing fiber of the present invention, particularly when the fiber is a polyester fiber, the effect of improving the adhesion to rubber and the operational stability in the treatment agent applying step is great.

The polyester fibers contain at least 90 mol% of polyethylene terephthalate (PET). In a preferred embodiment, the polyester is substantially all polyethylene terephthalate. Alternatively, the polyester contains as copolymer units a small amount of units based on ethylene glycol and one or more ester-forming components other than terephthalic acid or its derivatives. Specific examples of other ester-forming components that can be copolymerized with polyethylene terephthalate units include glycols such as diethylene glycol, trimetylene glycol, tetrameteren glycol, hexameteren glycol and the like, isophthalic acid, hexahydroterephthalic acid, dibenzoic acid Dicarboxylic acids such as acids, adipic acid, sebacic acid, azelaic acid and the like.

The molecular weight, single-filament fineness, single-filament number, physical properties, presence or absence of a fine structure additive, and polymer properties (such as terminal carboxyl group concentration) of these polyester fibers are not particularly limited.

In the method for producing the rubber / fiber bonding agent and the rubber reinforcing fiber of the present invention, the gum-up phenomenon is reduced, the operation stability (productivity) is excellent, and the adhesion to rubber is excellent. Rubber reinforcing fibers can be efficiently produced.

[0051]

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 The adhesive strength was measured by the adhesive strength-A method of JIS L 1017 (1983). That is, the fibers were embedded in unvulcanized rubber and press-vulcanized at 150 ° C. for 30 minutes. After cooling, the fiber was pulled out of the rubber block at a speed of 30 cm / min, and the pulling load was indicated in N / cm. (2) Peeling adhesion between plies (rubber adhesion rate, peeling force) A 2-ply treated cord is embedded in rubber as a cross ply (cord driving density of 28 wires / inch) forming an angle of 90 °, at 150 ° C. Press vulcanization was performed for 30 minutes, and after allowing to cool, both plies were peeled and measured at a pulling speed of 10 cm / min. The rubber adhesion rate is a value obtained by observing the cord peeled off from the rubber with the naked eye and expressing the portion where the rubber is adhered to the cord surface in percentage, and the peeling force is the force required for peeling in N / 2 cm. Things. As the rubber compound used for the above-mentioned adhesion evaluation, an unvulcanized rubber containing a natural rubber as a main component and containing a carcass was used. (3) Fatigue Resistance (Good Frit Disk Fatigue) According to JIS L 1017 (1983), two disks in which a rubber block filled with polyester fiber is inclined so that the elongation rate is 5% and the compression rate is 15%. And the percentage of strong residual strength after 100 hours of fatigue at 1705 rpm for 48 hours. 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 The cord is cut straight to 2 cm, and the bridge of Tensilon tensile tester (1 cm interval, φ: 0.6
mm) and a hook bar (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 Dirt) The scum 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. ×: Many scum sticks are observed.

Examples 1 to 3 Sorbitol polyglycidyl ether was added with water and emulsified using a homogenizer, and 4,4 blocked with ε-caprolactam
'-Diphenylmethane diisocyanate and vinyl pyridine-styrene-butadiene terpolymer rubber latex were each added at 10% by weight / 22% by weight / 6 solids.
To a solution having a concentration of 5.0% by weight mixed at a ratio of 8% by weight, sodium salt of lignosulfonic acid (Nippon Paper Industries Co., Ltd.)
The first bath treatment liquid was prepared by adding the respective amounts shown in Table 1 to 100 parts by weight of the solid content of the rubber latex.

In addition, resorcinol 1 was added in the presence of caustic soda.
A vinylpyridine-styrene-butadiene terpolymer rubber latex was mixed with an RF initial condensate obtained by reacting 1.50 mol of formalin with respect to 1 mol of RF initial condensate / rubber latex = 1/7 (solid (Part ratio) to give a 20% by weight liquid, aged at 25 ° C. for 24 hours, and 100 parts by weight of this RFL was added to an aqueous dispersion 10 of diphenylmethane-bis 4,4′-N, N′-diethylene urea. By adding parts by weight, a second treatment liquid having a solid content of 10% by weight was obtained.

On the other hand, two 1670 dtex multifilaments obtained by melt-spinning polyethylene terephthalate having a yarn viscosity of 0.95 and twisting were twisted at a twist number of 40 times / 10 cm and a twist rate of 40 times / 10 cm for a raw cord. I got

Next, the first treatment liquid was applied to the raw cord using a computer drip single dipping machine (manufactured by Ritzler, Inc.), and drained under the condition of an air wiper pressure of 0.15 kg / cm ^2. Followed by drying at 120 ° C. for 100 seconds, followed by 3 hours at 240 ° C.
Heat treated for 6 seconds.

Further, the second treatment liquid was applied, the liquid was drained under the condition of an air wiper pressure of 0.30 kg / cm ² , dried at 100 ° C. for 100 seconds, and subsequently dried at 240 ° C. for 60 seconds.
Heat treated for seconds.

The solid content of the first bath treatment solution of the obtained treatment cord was 1.2% by weight, and the solid content of the second treatment solution was 1.0% by weight. Table 1 shows the characteristic evaluation results of each processing code obtained in this manner.

[0058]

[Table 1]

Example 4 A mixture of 100% by weight of sorbitol polyglycidyl ether, 10% by weight of dioctyl sulfosuccinate sodium salt, water and emulsification using a homogenizer, and vinylpyridine-styrene-butadiene ternary A copolymer rubber latex was mixed with a 50% by weight / 50% by weight solid content, and a 15.0% by weight solution was mixed with a sodium salt of lignosulfonic acid to obtain a rubber latex having a solid content of 100% by weight. 1 part by weight was added to 2 parts by weight to prepare a first bath treatment liquid. The second treatment liquid used was the same as that used in Examples 1 to 3.

The solid content of the first bath treatment liquid of the obtained treatment cord was 3.2% by weight, and the solid content of the second treatment liquid was 1.0% by weight. Table 1 also shows the characteristic evaluation results of the processing codes thus obtained.

[Comparative Examples 1 to 3] When the sodium salt of lignosulfonic acid was not used in the composition of Example 1 (Comparative Example 1), the amount of the first treatment liquid applied was 0.3% by weight, and the first treatment was also performed. When the addition amount of the sodium salt of lignosulfonic acid was 12% by weight (Comparative Example 2), dioctyl sulfosuccinate sodium salt manufactured by Dai-ichi Kogyo was used as an anionic surfactant instead of the sodium salt of lignosulfonic acid. When 2 parts by weight (trade name: Neocol SW-30) is added to 100 parts by weight of the solid content of the rubber latex (Comparative Example 3), when the sodium salt of lignosulfonic acid is not used in the composition of Example 4 ( For Comparative Example 4), a processing code was obtained under the same processing conditions as in the example. Table 2 shows the characteristic evaluation results of each processing code obtained in this manner.
Shown in

[0062]

[Table 2]

[0063]

According to the present invention, it is possible to improve the operation stability by suppressing the gum-up phenomenon in the adhesive treatment agent applying step (dipping) without impairing the performance such as adhesion to rubber and fatigue resistance. Thus, a high-quality rubber reinforcing fiber can be efficiently obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09J 107/02 C09J 107/02 D02G 3/48 D02G 3/48 D06M 13/02 D06M 13/02 15/693 15/693 // B29K 21:00 B29K 21:00 61:00 61:00 D06M 101: 32 D06M 101: 32 F term (reference) 4F212 AA37 AA45 AC05 AD05 AD16 AD36 AH20 VA11 VD07 VD10 VD18 VL20 4J040 BA232 CA011 CA071 CA081 CA151 CA171 EC032 EC052 EC062 EC072 EC082 EC262 EF332 GA25 HC19 HC23 JB02 LA11 MA12 MA16 MB02 MB03 NA10 NA12 NA16 PA09 4L033 AA07 AB01 AC11 BA07 BA69 CA34 CA68 CA69 4L036 MA05 MA24 MA33 PA17 PA21 PA26 RA24 UA08

Claims (13)

[Claims] 1. An adhesive treating agent containing at least a rubber latex in a matrix component, wherein the sodium latex of lignosulfonic acid is contained in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of a solid content of the rubber latex. Rubber / fiber bonding agent. 2. The rubber / fiber bonding agent according to claim 1, wherein the matrix component does not contain a resorcinol-formaldehyde precondensate. 3. The matrix component according to claim 1, wherein the matrix component contains one or more compounds selected from the group consisting of a polyepoxide compound, a blocked polyisocyanate compound and an ethylene urea compound, in addition to the rubber latex. The adhesive treatment agent for rubber and fiber according to 1. 4. A rubber reinforcing fiber cord obtained by applying a rubber / fiber bonding agent to at least the surface of a synthetic fiber cord, wherein the lignosulfonic acid has a basic skeleton of phenylpropane represented by the following general formula: A fiber cord for rubber reinforcement, wherein the fiber cord surface is coated with an adhesive agent containing a sodium salt of the above. 5. The adhesive treatment agent applied to the surface of the synthetic fiber cord comprises an inner layer portion and an outer layer portion, wherein the matrix component of the adhesive treatment agent in the inner layer portion contains substantially no resorcinol-formaldehyde precondensate, 5. The rubber reinforcing fiber according to claim 4, wherein the matrix component of the partial adhesive treatment agent contains a resorcinol-formaldehyde precondensate. 6. The adhesive agent according to claim 4, wherein the adhesive treatment agent contains, as a matrix component, at least one selected from the group consisting of rubber latex, polyepoxide compound, blocked polyisocyanate compound and ethylene urea compound. The fiber cord for rubber reinforcement according to the above. 7. The fiber cord for rubber reinforcement according to claim 4, wherein the adhesive agent is attached in an amount of 0.8 to 6.0% by weight based on the weight of the fiber cord. . 8. The rubber reinforcing fiber cord according to claim 4, wherein the synthetic fiber cord is made of polyester. 9. The synthetic fiber cord is a cord obtained by twisting a polyester fiber.
The fiber cord for rubber reinforcement according to any one of the above. 10. The surface of a synthetic fiber cord according to claim 1 to 3.
A method for producing a fiber cord for rubber reinforcement, comprising applying the adhesive treatment agent according to any one of the above, followed by heat treatment. 11. A second treatment liquid containing a mixture of a resorcinol-formaldehyde precondensate and a rubber latex in a matrix component is further applied to the surface of the synthetic fiber cord,
The method for producing a fiber cord for rubber reinforcement according to claim 10, wherein heat treatment is performed. 12. The matrix component of the second treatment liquid comprises a mixture with a resorcinol-formaldehyde precondensate and a rubber latex and a blend with a blocked polyisocyanate compound and / or an ethylene urea compound. Item 12. A method for producing a fiber cord for rubber reinforcement according to item 11. 13. The method for producing a fiber cord for rubber reinforcement according to claim 10, wherein the synthetic fiber cord is made of polyester.