JP2541319B2 - Method for treating fiber material for rubber reinforcement - Google Patents

Description

The present invention relates to a method for treating a rubber-reinforcing fiber material, and particularly to a rubber obtained by suppressing foaming in a nip step after applying an adhesive liquid to the fiber material. There is little uneven adhesion of the adhesive to the reinforcing fiber material, and it has high and stable adhesive force with rubber,
The present invention also relates to a method for treating a fiber material, which is excellent in flexibility and provides a rubber-reinforcing fiber material in which deterioration of the fiber when embedded in rubber and repeatedly bent is suppressed.

[Conventional technology]

Various techniques have been conventionally known as treatment methods for improving the adhesion between the fiber material and the rubber. For example, as a method of treating nylon fibers, a method of treating with a mixture of resorcin-formalin resin and rubber latex, which is a good adhesive with rubber (hereinafter referred to as RFL), is known. As a method for treating the polyester fiber, which is difficult to adhere to, is treated with a first treatment bath containing a polyepoxide compound, a blocked polyisocyanate compound and a rubber latex in a specific ratio, and then
Method of treatment with a second treatment bath containing RFL (JP-A-60-24226)
However, there is also known a method of treating an aromatic polyamide fiber with a treatment liquid containing a blocked polyisocyanate compound as a main agent (JP-A-52-12397).

[Problems to be Solved by the Invention]

Polyester fibers and aromatic polyamide fibers treated by these methods have improved adhesiveness with rubber, but they often foam in the nip step after application of the adhesive, and the use of antifoaming agents such as silicone oil is unavoidable. It was found that the fiber material was lost or the obtained fiber material had a large amount of uneven adhesion of the adhesive, and the adhesive force with the rubber was unstable and varied widely.

[Means for solving the problem]

The above-described object of the present invention is to provide a fiber material with the following (A) to
It is characterized in that it is treated with a first treatment liquid containing the compound of (F), then heat treated, and then treated with a second treatment liquid containing the compounds of the above (B) and (D) and heat treated. This is achieved by the method of treating the rubber-reinforcing fiber material.

(A) Compound represented by the following general formula [I] (However, in the above formula [I], x is an integer of 10 to 60 and y is 0 to
The integer of 60 and n represent the integer of 1-3. ) (B) Blocked polyisocyanate compound (C) Polyepoxide compound (D) Mixture of resorcinol-formaldehyde precondensate and rubber latex (E) Partially hydrolyzed ammonium alkyl polyacrylate (F) General formula [II] ] The compound shown by (However, m and n in the above formula [II] each represent an integer of 0 to 30.) The fiber material of the present invention means a polyester fiber or poly-p-phenylene mainly containing ethylene terephthalate or butylene terephthalate as a repeating unit. Fiber materials known as tire cord materials other than steel, such as various aromatic polyamide fibers typified by terephthalamide, yarns of these fibers, cords obtained by twisting yarns, woven fabrics of cords, etc. Any form may be used.

The first step of the present invention is to treat the fiber material with the first treatment liquid.

Examples of the compound represented by the above general formula [I] contained in the first treatment liquid of the present invention include di (polyoxyethylene monostyrylphenyl) methane (formula [I]
X = 10-60), di (polyoxyethylene distyrylphenyl) methane (x = 10-60 in formula [I]), di (polyoxyethylene tristyrylphenyl) methane (formula [I] X = 10 to 60), di (polyoxyethylene / polyoxypropylene / monostyrylphenyl) methane (x = 10 to 60, y = 1 to 60 in the formula [I]), di (polyoxyethylene / Polyoxypropylene / distyrylphenyl) methane (x = 10 to 60, y = 1 to 60 in the formula), di (polyoxyethylene / polyoxypropylene / tristyrylphenyl) methane (x = 10 to 60 in the formula) , y = 1-60) and the like. These compounds can be used alone or in combination, and among these compounds, the compounds in the formulas where x = 13 to 40 and y = 1 to 10 are particularly preferable. The concentration of the compound represented by the above formula [I] in the first treatment liquid is usually adjusted to the range of 0.02 to 1.5% by weight. The compound represented by the above formula [I] is added to the first treatment liquid and mixed.
It may be dissolved, but it may be mixed or dissolved in advance with the compounds (B) to (E) and added to the first treatment liquid.

The blocked polyisocyanate compound contained in the first treatment liquid of the present invention is a reaction product of a polyisocyanate compound having two or more isocyanate groups in one molecule and a compound having an active hydrogen atom in one molecule. Yes,
As a specific example, hexamethylene diisocyanate, 2,
4-tolylene diisocyanate, 2,4-chlorophenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, ω,
ω '-(ditrimethylene thioether) diisocyanate, diisocyanates such as S-triazine triisocyanate, thiophosphoric acid tris (p-isocyanatephenyl) ester, triphenylmethane triisocyanate, diphenylmethane triisocyanate, butane-
1,2,2-Triisocyanate, trimethylolpropane tolylene diisocyanate trimer adduct, triisocyanates such as 2,4,4'-diphenyl ether triisocyanate, polymethylene polyphenyl isocyanate (including the case of crude diphenylmethane diisocyanate) Polyisocyanate compounds such as and phenols, cresols, phenols such as thiophenol, lactams such as ε-caprolactam and valerolactam, acetoxime,
Examples thereof include oximes such as methyl ethyl ketoxime and reaction products with ethyleneimine. Among these blocked polyisocyanate compounds, the ethyleneimine block body has almost no dissociation of ethyleneimine and regeneration of the active isocyanate group accompanied by normal heating,
The main component of the reaction in the adhesive is due to the opening of the aziridine ring, and in other blocked polyisocyanate compounds, the active hydrogen group-containing compound dissociates by heating, and the active isocyanate group regenerates and reacts accordingly. Is. The concentration of the blocked polyisocyanate compound in the first treatment liquid may be usually 1.0 to 1.6% by weight.

The polyepoxide compound contained in the first treatment liquid of the present invention is a compound having two or more epoxy groups in one molecule, and specifically, glycerol, pentaerythritol, sorbitol, ethylene glycol, polyethylene glycol, Reaction products of polyhydric alcohols such as propylene glycol and polypropylene glycol with halogen-containing epoxides such as epichlorohydrin, resorcin, bis (4-hydroxyphenyl) dimethylmethane, phenol / formalin resin, resorcin / formalin resin, etc. Obtained by oxidizing unsaturated bond moieties such as reaction products of hydric phenols with halogen-containing epoxides, bis (3,4-epoxy-6-methyl-dicyclohexylmethyl) adipate, and 3,4-epoxycyclohexene epoxide. From It refers to that polyepoxide compounds, and the like. Particularly preferably, a reaction product of a polyhydric alcohol and epichlorohydrin (polyglycidyl ether compound of polyhydric alcohol) is preferably used. These polyepoxide compounds may be used alone or in combination of several kinds. These polyepoxide compounds are preferably dissolved in water or emulsified / dispersed in water by using a surfactant, because they can be uniformly mixed with the first treatment liquid, and are therefore preferable.
The concentration of the polyepoxide compound in the first treatment liquid is 0.5 to
It may be used by blending it in the range of 5.0% by weight.

RFL contained in the first treatment liquid of the present invention is an initial condensate obtained by reacting resorcin and formalin under an acid or alkali catalyst, natural rubber latex, styrene-butadiene copolymer latex, nitrile rubber latex, It is a mixture with one or several kinds of rubber latex from chloroprene rubber latex, vinyl pyridine, styrene, butadiene, terpolymer latex, etc., and is used after aging at 10 ° C to 30 ° C for 5 hours or more. The amount ratio of the resorcin-formalin initial condensate and the rubber latex is 4 to 96 to 40 to 60 in terms of solid content weight ratio.
Is preferred. The concentration of the RFL solid content in the first treatment liquid may be usually mixed and used in the range of 2 to 10% by weight.

The partially hydrolyzed ammonium of polyacrylic acid alkyl ester contained in the first treatment liquid of the present invention is obtained by partially hydrolyzing / ammonizing an alkyl ester of polyacrylic acid having a degree of polymerization of 300 to 20000. Examples thereof include those obtained by partially hydrolyzing and ammoniumating methyl acrylate, polyethyl acrylate, polybutyl acrylate, polypropyl acrylate, and the like. The concentration of the partially hydrolyzed ammonium polyacrylic acid alkyl ester in the first treatment liquid is usually adjusted to 0.1 to 3.0% by weight. The above-mentioned partially hydrolyzed ammonium polyacrylic acid alkyl ester may be added as it is or may be prepared in advance as an aqueous solution. After adding a predetermined amount to the above concentration, stirring and dissolving. Partially hydrolyzed ammonium of polyacrylic acid alkyl ester may be previously dissolved in a blocked polyisocyanate dispersion, polyepoxide compound emulsion, RFL, etc., [I]
It may be dissolved in these together with the formula compound.

(F), which is contained in the first treatment liquid of the present invention, is a compound represented by the following general formula [II], which is 2,4,7,9-tetrahydrofuran in which the sum of m and n in the formula [II] is 0. Methyl-5-decyne-4,7-diol, 2,4,7,9- in which the sum of m and n in the formula [II] is 1 to 60
It is an ethylene oxide adduct of tetramethyl-5-decyne-4,7-diol, and one or more of these compounds can be used, but especially 2,4,7,9-tetramethyl-5
-Decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7 in which the sum of m and n in the formula [II] is 1 to 5
It is preferable to use an ethylene oxide adduct of diol because the effect of suppressing foaming, which is one of the objects of the present invention, is further enhanced. The concentration of the compound represented by the formula [II] in the first treatment liquid is adjusted to 0.001 to 3% by weight. The compound represented by the formula [II] alone or dissolved in a water-soluble organic solvent such as ethylene glycol or alcohol and added to the first treatment liquid, or previously dissolved in a blocked polyisocyanate dispersion liquid, polyepoxide compound emulsion, RFL, etc. Alternatively, it may be dissolved in these together with the compound of the formula [I].

Other compounds such as cyanuric acid, isocyanuric acid, and 2,4,6-ethyloyl-S are contained in the first treatment liquid of the present invention.
-Triazine, 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate, triallyl cyanurate, trihydroxyethyl isocyanurate, and other triazine compounds, resorcin / p-chlorophenol / formalin condensate, poly One or more compounds selected from (resorcin polysulfide) and the like may be contained. The mixing order of the above-mentioned compounds contained in the first treatment liquid is not particularly limited and can be arbitrarily performed.

The application of the first treatment liquid is performed by a method such as coating, spraying or dipping. The application rate of the first treatment liquid to the fiber material is preferably 0.3 to 10% by weight based on the dry material. The fibrous material to which the first treatment liquid has been applied is then heat treated. Usually, the heat treatment is divided into drying at a relatively low temperature in hot air and high temperature treatment, but the drying can be omitted. Drying during the heat treatment is 40 ° C to 17
It is carried out at 0 ° C for 30 seconds to 10 minutes. High temperature treatment is 170 ℃
30 seconds ~ 10 minutes at 270 ℃, more preferably 180 ℃ ~
It is recommended to carry out at 255 ℃ for 30 seconds to 10 minutes.

Thus, the fiber material which has been subjected to the heat treatment by applying the first treatment liquid is subjected to the heat treatment by applying the second treatment liquid of the present invention.

The blocked polyisocyanate compound (B) contained in the second treatment liquid of the present invention is the same as the blocked polyisocyanate compound contained in the above first treatment liquid. The concentration in the second treatment liquid may be usually 1.0 to 6.0% by weight.

(D) which is contained in the second treatment liquid in the present invention
The RFL is the same as the RFL in the above-mentioned first treatment liquid, and the amount ratio of the resorcin-formalin initial condensation product and the rubber latex is preferably in the range of 4:96 to 40:60 in terms of solid content weight ratio. The solid content concentration of RFL in the second treatment liquid is 3 to 2
It is used by blending it in the range of 0% by weight.

Other compounds, such as cyanuric acid, isocyanuric acid, 4,6-ethyloyl-S-, can be used in the second treatment liquid of the present invention.
Triazine, 1,3,5-triacryloylhexahydro-
Triazine compounds such as S-triazine, triallyl isocyanurate, triallyl cyanurate, trihydroxyethyl isocyanurate, etc., resorcin / p-chlorophenol / formalin condensate, poly (resorcin / polysulfide), first treatment solution It is also possible to include one or more compounds selected from the compounds represented by the general formula [I], polyepoxide compounds, partially hydrolyzed ammonium polyacrylic acid alkyl ester and the like. The order of adding the above-mentioned various compounds contained in the second treatment liquid is not particularly limited and can be arbitrarily performed.

The application of the second treatment liquid is performed by a method such as coating, spraying or dipping. The rate of application of the second treatment liquid to the fiber material is preferably 0.1 to 10% by weight based on the dry material. The fibrous material to which the second treatment liquid has been applied is then heat treated. Usually, the heat treatment is divided into drying at a relatively low temperature in hot air and high temperature treatment, but the drying can be omitted. Drying during the heat treatment is 40 ° C to 170
30 seconds to 10 minutes at ℃. High temperature treatment is 170 ℃ -2
30 seconds ~ 10 minutes at 60 ℃, more preferably 180 ℃ ~ 2
It is recommended to carry out at 55 ° C for 30 seconds to 10 minutes.

The blocked polyisocyanate compound contained in the above-mentioned first and second treatment liquids is added to water or a medium containing water as a main component together with the compounds represented by the formulas [I] and [II], It can be finely dispersed by a known dispersion method and used as a blocked polyisocyanate compound dispersion. Further, in preparing the blocked polyisocyanate compound dispersion, in addition to the compounds represented by the formulas [I] and [II], known anion and nonionic surfactants can be used in combination, if necessary. It is preferable that most of the particles of the blocked polyisocyanate compound in the blocked polyisocyanate dispersion have a particle size of 10 μm or less, and the average particle size is in the range of 0.1 to 5.0 μm.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
In addition, each measured value in an Example is measured by the following method.

Foaming amount: 45 ml of the first treatment liquid was put into a 100 ml graduated cylinder, and a glass tube for bubble generation (inner diameter 6 mm, from the bottom of the graduated cylinder)
The volume of foam (ml) after introducing air at 40 ml / min for 3 minutes is expressed in volume (ml) through an outer diameter of 8 mm and a glass filter is attached to the tip).
Show good.

T-initial adhesive strength: The treated fiber material cord is embedded in unvulcanized rubber,
The load is expressed in kg / cm when the cord was pulled out from the rubber block at a speed of 20 cm / min after being subjected to press vulcanization at a temperature of 140 ° C. and a pressure of 50 kg / cm ² for 40 minutes and allowed to cool to room temperature.

Variation in adhesive strength: The above initial adhesive strength was measured for 32 rubber blocks and the difference between the highest and lowest measured values was shown.

Adhesive unevenness of adhesion: 50 fibrous material cords after processing were aligned for each 1m, and the adhesive adhesion unevenness was visually judged, and those with a lot of unevenness were marked with X, and those with no unevenness or very little unevenness were marked with a circle. It is a thing.

Flexibility: It is measured by the Gurley method, and the smaller the value, the softer it is.

Fatigue resistance in rubber (Goodrich disc fatigue): A rubber block obtained by embedding a treated fiber material in a vulcanized polyester fiber has an elongation rate of 6%, a compression rate of 18%, and a poly-
The p-phenylene terephthalamide fiber was attached around two disks tilted so that the elongation rate was 0% and the compression rate was 15%, and the strength remaining rate after repeated fatigue at 1705 rpm for 48 hours was shown as a percentage. It is a thing.

Examples 1 and Comparative Examples 2 to 5 [I] Containing di (polyoxyethylene tristyrylphenyl) methane as a formula compound, and a methylethylketoxime block of 4,4'-diphenylmethane diisocyanate as a blocked polyisocyanate compound. , An aqueous solution containing 2,4,7,9-tetramethyl-5-decyne-4,7-diol containing polyacrylic acid alkyl ester partially hydrolyzed ammonium (hereinafter referred to as an aqueous solution) is prepared as follows. Obtained.

19 parts by weight of di (polyoxyethylene tristyrylphenyl) methane (x = 28, y = 0 in the formula [I]), 2,4,7,
A ball mill was charged with 1 part by weight of 9-tetramethyl-5-decyne-4,7-diol, 200 parts by weight of 4,4'-diphenylmethane diisocyanate methylethylketoxime block, and 743 parts by weight of water, and the mixture was charged at 200 rpm for 36 hours. After the treatment, 28.5 parts by weight of a 20% by weight aqueous solution of partially hydrolyzed ammonium butyl polyacrylate (degree of polymerization 3000) was added to 760 parts by weight of the liquid extracted from the ball mill, and the mixture was stirred for 1 hour.

On the other hand, an aqueous solution of a polyepoxide compound (hereinafter referred to as an aqueous solution) was obtained as follows. 940 parts of water was added to 60 parts by weight of sorbitol polyglycidyl ether, and stirred with a homomixer at 2000 rpm for 10 minutes.

Further, an RFL aqueous solution was obtained as follows. To a solution prepared by adding 5.0 parts by weight of 1% NaOH aqueous solution to 396.6 parts by weight of water, and dissolving 18.5 parts by weight of resorcinol, further adding 27.2 parts by weight of 37% formalin aqueous solution and mixing, and aging at 25 ° C for 8 hours, Nipol 2510FS, a 40% by weight latex of vinyl pyridine / styrene / butadiene terpolymer (product of Zeon Corporation) 278.8 parts by weight, and 40% by weight latex of a styrene / butadiene copolymer, Nipol
Add LX-110 (product of Zeon Corporation) 142.0 parts by weight to 25 ° C.
It was aged for 16 hours.

Then, the first treatment liquid was prepared as follows. 140 parts by weight aqueous solution, 235 parts by weight aqueous solution, 585 RFL aqueous solution
By weight, 185 parts by weight of water were mixed and sufficiently stirred.

Further, the second treatment liquid was prepared as follows. 45 parts by weight of the aqueous solution, 455 parts by weight of the RFL aqueous solution and 400 parts by weight of water were mixed and sufficiently stirred.

On the other hand, in a mixed solvent of phenol / 4 ethane (1/1 weight ratio), polyethylene terephthalate chips with an intrinsic viscosity of 1.00 measured at 20 ° C were melt-spun from a spinneret with 288 holes to obtain 6000 denier undrawn. A spinning oil containing a fatty acid ester and a nonionic surfactant as main components was applied to the yarn with an oiling roller, and a hot drawing pin of 80 ° C and 170 ° C were used.
Was drawn 4 times by using the slit heater of No. 1 and heat-treated at the same time to obtain a drawn yarn of 1500 denier. The thus-obtained two drawn yarns were respectively subjected to lower twist and upper twist 40 times / 1
Twisted to 0 cm and coded.

This cord was immersed in the first treatment liquid, dried at 80 ° C. for 3 minutes, and then heat-treated at 190 ° C. for 90 seconds. Thus, the cord treated with the first treatment liquid and heat-treated is dipped in the second treatment liquid.
After drying at 0 ° C for 2 minutes, heat treatment was performed at 250 ° C for 90 seconds. The adhesive application rate to the cord was 3.8% by weight of the first treatment and 1.1% by weight of the second treatment, respectively, based on the dry solid content, relative to the untreated cord. Table 1 shows the evaluation results of the adhesive adhesion unevenness and various performances of the adhesive treatment cord thus obtained and the foamability of the first treatment liquid. The composition of the rubber compound used for measuring T-initial adhesive strength and fatigue resistance in rubber is shown below.

Natural rubber (RSS # 1) 70 (parts by weight) SBR (JRS1501) 30 (parts by weight) SRF carbon black 40 (parts by weight) Stearic acid 2 (parts by weight) Sulfur 2 (parts by weight) Zinc white 5 (parts by weight) 2 2,2'-dithiobenzothiazole 2 (parts by weight) Naphthenic acid process oil 3 (parts by weight) For the purpose of comparison, when the aqueous liquid of Example 1 was prepared, di (polyoxyethylene / tristyrylphenyl) methane ([I] In the formula, x = 28, y = 0) and 2,4,7,9-tetramethyl-5-decyne-4,7-diol were not added, but 20 parts by weight of sodium naphthalenesulfonate was added (comparison). Example 1), 235 parts by weight of water was added to the first treatment liquid of Example 1 instead of adding the aqueous liquid (Comparative Example 2), and 4,4′-when preparing the aqueous liquid of Example 1. Methyl ethyl ketoxime block of diphenylmethane diisocyanate Instead of not adding 200 parts by weight of water (Comparative Example 3), 28.5 parts by weight of water was added instead of adding the partially hydrolyzed ammonium aqueous solution of polybutyl acrylate during the preparation of the aqueous solution of Example 1. (Comparative Example 4), an adhesive obtained in the same manner as in Example 1 except that 200 parts by weight of water was added (Comparative Example 5) instead of adding the RFL aqueous solution when preparing the first treatment liquid. The adhesive adhesion unevenness of the treatment code, various performance evaluation results, and the foamability of the first treatment liquid are shown in Table 1.

Examples 2 to 11 Instead of di (polyoxyethylene tristyrylphenyl) methane (x = 28, y = 0 in the formula [I]) contained in the aqueous liquid in Example 1, di (polyoxy) was used. Using ethylene / polyoxypropylene / tristyrylphenyl) methane (x = 18, y = 3 in the formula [I] (Example 2), di (polyoxyethylene / monostyrylphenyl) methane ([I] ] (X = 20, y = 0) in the formula (Example 3) is used, which is contained in the aqueous liquid.
Instead of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-
Ethylene oxide adduct of diol (m + in the formula [II]
n = 4) 2 parts by weight were used (Example 4).
Using 3 parts by weight of an ethylene oxide adduct of 4,7,9-tetramethyl-5-decyne-4,7-diol (m + n = 10 in the formula [II]) (Example 5), similarly 2, In Example 1, 4 parts by weight of 4,7,9-tetramethyl-5-decyne-4,7-diol ethylene oxide adduct (m + n = 30 in the formula [II]) was used (Example 6). Instead of the partially hydrolyzed ammonium butyl polyacrylate contained in the aqueous liquid, the partially hydrolyzed ammonium polymethyl acrylate was used (Example 7), Example 1
Of blocked polyisocyanate compound of aqueous liquid in ε-of 4,4'-diphenylmethane diisocyanate
Substituting caprolactam block (Example 8),
Similarly, the ethyleneimine block of 4,4'-diphenylmethane diisocyanate was replaced (Example 9), and the blocked polyisocyanate compound in the aqueous liquid added to the first treatment liquid in Example 1 was replaced with 4,4'-diphenylmethane. The ethyleneimine block of diisocyanate was changed, and the second treatment liquid was the same as in Example 1 (Example 10). The blocked polyisocyanate compound in the aqueous liquid added to the second treatment liquid in Example 1 was used. 4,4'-
With the exception that the ethyleneimine block of diphenylmethane diisocyanate was used and the first treatment liquid was the same as in Example 1 (Example 11), there was uneven adhesion of the adhesive in the adhesive treatment cord obtained in the same manner as in Example 1. Various performance evaluation results and the foamability of the first treatment liquid are shown in Table 1.

As is clear from Table 1, the cord obtained by the method of the present invention has less unevenness in adhesive adhesion, has flexibility, excellent fatigue resistance in rubber, and high and stable adhesive force with rubber. In addition, it is suitable as a tire cord, and at the same time, the foaming of the first treatment liquid is small, which is an excellent method.

Examples 12-22, Comparative Examples 6-10 The cords made of polyethylene terephthalate fibers in Examples 1-11 and Comparative Examples 1-5 were made into poly-p.
− A cord made of phenylene terephthalamide fiber (DuPo
nt company product "Kevlar", 1500 denier, 1000 filaments ×
2, Examples 1 to 11 except that the lower twist 40 and upper twist 40)
And an adhesive treatment cord obtained in the same manner as Comparative Examples 1 to 5 (Example 1 corresponds to Example 12, Example 2 corresponds to Example 13).
In the same order, Examples 3 to 11 correspond to Examples 14 to 22, respectively. Comparative Example 1 corresponds to Comparative Example 6,
Comparative Example 2 corresponds to Comparative Example 7, hereinafter, Comparative Examples 3 to 5 correspond to Comparative Examples 8 to 10 in the same order.)
Table 2 shows the evaluation results of the adhesive adhesion unevenness and various performances and the foamability of the first treatment liquid.

As is clear from Table 2, the cord obtained by the method of the present invention has little unevenness in adhesive adhesion, has flexibility, excellent fatigue resistance in rubber, and high and stable adhesive force with rubber. In addition, it is suitable as a tire cord, and at the same time, the foaming of the first treatment liquid is small, which is an excellent method.

[Effects of the Invention] The rubber-reinforcing fiber material obtained by the method of the present invention has less foaming in the nip step after application of the treatment liquid, and the obtained rubber-reinforcing fiber material has less uneven adhesion of the adhesive, Highly adhesive, stable, flexible, embedded in rubber,
It is suitable as a rubber-reinforcing fiber material because it improves fatigue when repeatedly bent.

Claims (1)

(57) [Claims] 1. A fiber material is treated with a first treatment liquid containing the following compounds (A) to (F), then heat treated, and then containing the compounds shown in the following (B) and (D). A method for treating a rubber-reinforcing fiber material, which comprises treating with a second treatment liquid and heat-treating. (A) Compound represented by the following general formula [I] (However, in the above formula [I], x is an integer of 10 to 60 and y is 0 to
The integer of 60 and n represent the integer of 1-3. ) (B) Blocked polyisocyanate compound (C) Polyepoxide compound (D) Mixture of resorcinol / formalin resin and rubber latex (E) Partially hydrolyzed ammonium polyacrylate alkyl ester (F) In the following general formula [II] Compound shown (However, m and n in the above formula [II] each represent an integer of 0 to 30.)