JPH0397965A - Treating of fiber material for rubber reinforcement - Google Patents

Abstract

PURPOSE:To reduce bubbling in nipping process and enhance adhesion to a rubber by treating a fiber material with first a treating solution containing specific six species of compounds, heat-treating, treating with a second treating solution containing specific two species of compounds and heat-treating. CONSTITUTION:A fiber material is treated with a first treating solution containing (A) a compound expressed by formula I (x is 10-60; y is 0-60; n is 1-3), (B) a blocked polyisocyanate compound, (C) a polyepoxide compound, (D) a mixture of resorcin.formalin resin and rubber latex, (E) partially hydrolyzed ammonium of polyacrylic alkyl ester and (F) a compound expressed by formula II (m and n are 0-30) and heat-treated, then treated with a second treating solution containing compounds of component B and D, thus heat-treated.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for treating fiber materials for rubber reinforcement, and in particular to a method for treating fiber materials for rubber reinforcement, in which foaming is suppressed in the nip process after applying an adhesive liquid to the fiber materials, and the resulting rubber is 11 There is little uneven adhesion of the adhesive to the reinforcing fiber material, and it has a high and stable adhesive force with rubber.
The present invention also relates to a method of processing a fiber material for rubber reinforcement, which provides a fiber material for reinforcing rubber that has excellent flexibility and suppresses deterioration of the fibers when embedded in rubber and subjected to repeated bending.

[Conventional technology]

Various techniques are conventionally known as treatment methods for improving the adhesion between fiber materials and rubber. For example, a known method for treating nylon fibers is to treat them with a mixture of resorcin formalin resin and rubber latex (hereinafter referred to as RFL), which is a good adhesive with rubber. A method for treating polyester fibers that are difficult to adhere to is to treat them with a first treatment bath containing a polyeboxide compound, a blocked polyisocyanate compound, and rubber latex in a specific ratio, and then with a second treatment bath containing RFL. Method (Unexamined Japanese Patent Publication 1986)
There is also known a method in which aromatic polyamide fibers are treated with a treatment liquid containing a blocked polyisocyanate compound as the main agent (Japanese Patent Laid-Open No. 12397/1982).

[Problem to be solved by the invention]

Although polyester fibers and aromatic polyamide fibers treated by these methods have improved adhesion to rubber, they often foam during the nipping process after applying the adhesive.
I learned that it was necessary to use antifoaming agents such as silicone oil, that the resulting fiber material had a lot of uneven adhesive adhesion, and that the adhesive strength with rubber was unstable and varied.

[Means to solve the problem]

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

(A) Compound represented by the following general formula [I] (However, in the above formula [I], X represents an integer of 10 to 60, y represents an integer of 0 to 60, and n represents an integer of 1 to 3.) B) Blocked polyincyanate compound (C) Polyeboxide compound (D>Mixture of resorcin/bormaldehyde initial condensate and rubber latex (E>Partially hydrolyzed ammonium of polyacrylic acid alkyl ester (F)) Following general formula (II) ) (However,
m and n in the above formula [■] each represent an integer of 0 to 30. ) The fiber material of the present invention is mainly ethylene terephthalate. It is a fiber material known as a tire cord material other than steel, such as polyester fiber having a repeating unit of polyester or butylene terephthalate, and various aromatic polyamide fibers represented by poly p-phenylene terephthalamide. It may be of any form, such as a coarse thread, a cord made of twisted threads, or a woven fabric made of a cord.

The first step of the invention is to treat the fibrous material with a first treatment liquid.

The above general formula (I) contained in the first treatment liquid of the present invention
), for example, di(bolyoxyethylene monostyrylphenyl) methane (x = 10 to 60 in formula (I)), di(bolyoxyethylene monostyrylphenyl) methane (formula [ I] x = 10 ~ 60
), di{polyoxyethylene tristyrylphenyl}
Methane (x in formula (I) = 10-60>, di(boroxyethylene polyoxypropylene monostyrylphenyl) methane (x = 10-60 in formula [I), y = l~
60〉. Di(polyoxyethylene/polyoxypropylene/distyrylphenyl)methane (x=10~・
60. y=1 to 60), di(polyoxyethylene/boroxypropylene/tristyrylphenyl)methane (in the formula, x=10 to 60, y=1 to 60), and the like.

These compounds can be used alone or in combination, but among these compounds, x-13 in the formula
˜40, and compounds where y=l˜10 are particularly preferred.

The concentration of the compound represented by the above formula [■] in the first treatment liquid is usually adjusted to a range of 0.02 to 1.5%. The compound represented by formula (I) above is added to the first treatment liquid and mixed.
Although it is sufficient to dissolve it, it is also possible to mix or dissolve it in advance with the compounds (B) to (E) above and add it to the first treatment liquid.

The blocked polyisocyanate compound contained in the treatment liquid No. 1 of the present invention is a reaction product of a polyisocyanate compound having two or more incyanate groups in one molecule and a compound having an active hydrogen atom in the molecule. Specific examples include hexamethylene diisocyanate, 2.
Diisocyanates such as 4-tolylene diisocyanate, 2,4-chlorophenylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, ω, ω-11 (ditrimethylene thioether) diisocyanate, S-triazine Triisocyanate, thiophosphoric acid tris(p-isocyanate phenyl) ester, triphenylmethane triisocyanate, diphenylmethane triisocyanate, butane-1,2,2-triisocyanate, trimethylolpropane tolylene diisocyanate teradduct, 2.
4.4 Triisocyanates such as diphenyl ether triisocyanate, polyisocyanate compounds such as polymethylene borifhenyl isocyanate (including the case of crude diphenylmethane diisocyanate), phenols such as phenol, cresol, thiophenol, etc.
Examples include lactams such as caprolactam and valerolactam, oximes such as acetoxime and methyl ethyl ketoxime, and products reacted with ethyleneimine. Among these blocked polyisocyanate compounds, in the case of ethyleneimine block compounds, the dissociation of ethyleneimine and the accompanying regeneration of active incyanate groups hardly occur under normal heating, and the main reaction in the adhesive is the aziridine ring. In other blocked polyisocyane-1~ compounds, the active hydrogen group-containing compound dissociates upon heating, and the active isocyanate group is accordingly regenerated and reacts. The concentration of the blocked polyisocyanate compound in the treatment solution No. 1 is usually 1.0 to 1.6% by weight.
All you have to do is mix it up.

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. Pentaerythrol, sorbitol, ethylene glycol. Polyethylene glycol. 1 Reaction of polyhydric alcohols such as robylene glycol and polypropylene glycol with halogen-containing epoxides such as shrimp chlorohydrin, resorcinol, bis(4-hydroxyphenyl)dimethylmethane, phenol/formalin resin, resorcinol・Reaction products of polyhydric phenols such as formalin resin and the halogen-containing epoxides, bis(3,4.-epoxy-6-methyl-dicyclohexylmethyl) adipate, 3,4-epoxycyclohexene eboxide, etc. Refers to polyepoxide compounds etc. obtained by oxidizing unsaturated bond parts. Particularly preferably, reaction products of polyhydric alcohols and epichlorohydrin (polyglycidyl ether compounds of polyhydric alcohols) are used.

These polyeboxide compounds may be used alone or in combination. It is preferable to use these polyepoxide compounds by dissolving them in water or by emulsifying and dispersing them in water using a surfactant, since these can be uniformly mixed into the first treatment liquid.

The concentration of the polyeboxide compound in the treatment solution No. 1 is 0.5
It may be used in a range of 5.0% to 5.0%.

The RFL contained in the first treatment liquid of the present invention is an initial condensation product obtained by reacting resorcin and formalin under an acid or alkali catalyst, natural rubber latex, styrene-butadiene-cobolymer latex, and nitrile rubber latex. , chloroprene rubber latex, vinylpyridine/styrene/butadiene/turbolimer latex, etc., and is used after being aged at 10°C to 30°C for 5 hours or more. The weight ratio of the resorcinol/formalin initial shrinkage product to the rubber latex is preferably in the range of 4:96 to 40:60 in terms of solid content weight ratio. The concentration of the RFL solid content in the first treatment liquid may normally be adjusted to a 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 partially hydrolyzed and ammoniumized polyacrylic acid alkyl ester with a degree of polymerization of 300 to 20,000,
For example, polymethyl acrylate, polyethyl acrylate.
Examples include those obtained by partially hydrolyzing and ammonizing polybutyl acrylate, probyl polyacrylate, etc. The concentration of the above partially hydrolyzed ammonium of polyacrylic acid alkyl ester in the first treatment liquid is usually 0.1 to 3.
Adjust to 0% by weight. The above partially hydrolyzed ammonium of polyacrylic acid alkyl ester may be added as it is or may be made into an aqueous solution in advance, and after adding a predetermined amount to the above concentration, it is stirred and dissolved.

The partially hydrolyzed ammonium of polyacrylic acid alkyl ester may be dissolved in advance in a blocked polyisocyanate dispersion, polyeboxide compound emulsion, RFL, etc., or may be dissolved therein together with the compound of formula [I].

(F) contained in the first treatment liquid of the present invention is a compound represented by the following general formula [■], in which the sum of m and n is O, 2.4,7.9-tetra Methyl-5-decyne-4
．． 7-diol, CII) where the sum of m and n in the formula is 1 to 60
2,4,7.9-tetramethyl-5-decyne-4,7
It is an ethylene oxide adduct of monodiol, and one or more of these compounds can be used, but especially 2,4
, 7.9-tetramethyl-5-decyne-4,7-diol and (n) 2.4,7 in which the sum of m and n in the formula is 1 to 5
．． It is preferable to use an ethylene oxide adduct of 9-tetramethyl-5-decyne-4,7-diol because it further enhances the effect of suppressing foaming, which is one of the objects of the present invention. [■] The concentration of the compound represented by the formula in the first treatment solution is
Adjust to 0.001-3%. The compound represented by formula CII) may be added alone or dissolved in a water-soluble organic solvent such as ethylene glycol or alcohol to the first treatment solution, or may be dissolved in advance in a blocked polyisocyanate dispersion, polyepoxide compound emulsion, RFL, etc. or may be dissolved therein together with the compound of formula [I].

The first treatment liquid of the present invention contains other compounds, such as cyanuric acid, isocyanuric acid, 2.4.6-ethyloyl-S-triazine, 1.3.5-triacryloylhexahydro-S-triazine, triallylisocyanurate. , triazine compounds such as triallyl cyanurate and trihydroxyethyl isocyanurate, resorcin・p-
It is also possible to contain one or more compounds selected from chlorophenol/formalin condensate, poly(resorcinol/polysulfide), and the like. The order of mixing the above-mentioned compounds contained in the first treatment liquid is not particularly limited,
It can be done arbitrarily.

The application of the first treatment liquid is carried out by coating, bubbling, dipping, or the like. The application rate of the first treatment liquid to the fiber material is preferably 0.3 to 10% by weight based on the dry weight ratio of the fiber material.

The fibrous material to which the treatment liquid has been applied is then heat-treated, and the heat treatment is usually carried out in hot air by dividing it into drying at a relatively low temperature and high-temperature treatment, but the drying can also be omitted. Drying during the heat treatment was performed at 40°C to 170°C.
It is carried out for 0 seconds to 10 minutes. In addition, high temperature treatment is from 170℃
It is preferably carried out at 270°C for 30 seconds to 10 minutes, more preferably at 180°C to 255°C for 30 seconds to 10 minutes.

The fiber material thus applied with the first treatment liquid and heat-treated is then applied with the second treatment liquid of the present invention and heat-treated.

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 first treatment liquid. The concentration in the second treatment liquid is usually adjusted to 1.0 to 6.0%.

(D)R contained in the second treatment liquid in the present invention
FL is the same as RFL in the above-mentioned first processing solution, and the ratio of the resorcinol/formalin initial condensate to the rubber latex is preferably in the range of 4:96 to 40:60 in terms of solid content weight ratio. The solid content of RFL in the second treatment liquid is adjusted to a concentration of 3 to 20% by weight.

The second treatment liquid of the present invention contains other compounds, such as cyanuric acid, incyanuric acid, 4.6=ethyloyl-S-
Triazine, 1,3.5-triacryloylhexahydro S-triazine, triazine compounds such as triallyl isocyanurate, triallyl cyanurate trihydroxyethyl isocyanurate, resorcinol/p-chlorophenol/formalin condensate, poly(resorcinol/ polysulfide), a compound represented by the general formula [■], a polyeboxide compound, polyacrylic acid alkyl ester partially hydrolyzed ammonium, etc. contained in the treatment liquid No. You can also do that. The order in which the above-mentioned various compounds contained in the second treatment liquid are added is not particularly limited and can be added arbitrarily.

Application of second treatment liquid. This can be done by coating, spray dipping, or other methods. The application rate of the second treatment liquid to the fiber material is preferably 0.1 to 10% by weight based on the dry weight ratio of the fiber material. The fiber material to which the second treatment liquid has been applied is then subjected to a dry treatment, which is usually divided into drying at a relatively low temperature and high temperature treatment in natural air, but the drying may be omitted. can. Drying during the heat treatment is at 40℃~
This is carried out at 170°C for 30 seconds to 10 minutes. Further, the high temperature treatment is carried out at 170°C to 260°C for 30 seconds to 10 minutes, more preferably at 180°C to 255°C for 30 seconds to 10 minutes.

The blocked polyisocyanate compound contained in the first and second treatment liquids described above may be added to water or a medium containing water as a main component together with the compounds represented by formulas [■] and (I[). Then, it can be finely dispersed by a known dispersion method and used as a blocked polyisocyanate compound dispersion. In addition, in preparing the blocked polyisocyanate compound dispersion, in addition to the compounds represented by formulas [I] and [■], known anionic and nonionic surfactants can be used in combination as necessary. The particle size of the fine particles made of the blocked polyisocyanate compound in the blocked polyisocyanate dispersion is mostly 10 μm or less, and the average particle size is 0.1 to 5.0 μm.
The range is preferably m.

〔Example〕

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

Holding: Put 45 ml of the first treatment liquid into a 100 ml measuring cylinder, and blow air at 40 ml/min from the bottom of the graduated cylinder through a glass tube for bubble generation (inner diameter 6I11111, outer diameter 81+1111, with a glass filter at the tip). The amount of bubbles after introduction for 3 minutes is expressed by volume (m1), and the smaller the value, the less bubbles are generated and the better the result.

Eni-period lid attachment: The treated fiber material cord is embedded in unvulcanized rubber, press-vulcanized at a temperature of 140°C and a pressure of 50 KMcJ for 40 minutes, and after cooling to room temperature, the cord is removed from a rubber block for 20 minutes.
The load when pulled out at a speed of cm/min is IGI/cm
It is expressed as

The above initial adhesive strength was tested on 32 rubber blocks, and the difference between the highest and lowest measured values is shown.

Fifty fiber material cords of 1m each after treatment are arranged, and the uneven adhesion of the adhesive is judged with the naked eye.Those with a lot of unevenness are marked as ×, and those with no or very little unevenness are marked as ○. It is expressed as

It is measured using the Gurley method, and the smaller the value, the more flexible it is.

Rubber ni G (Goodrich method disk fatigue): A rubber block in which the treated fiber material is embedded and vulcanized has an elongation rate of 6% and a compression rate of 18% for polyester fibers, and an elongation rate of 18% for poly p-phenylene terephthalamide fibers. The remaining strength is shown as a percentage after being placed around two disks tilted so that the compression rate is 15% and subjected to repeated fatigue at 1705 rpm for 48 hours. .

Example 1, Comparative Examples 2 to 5 [I] Contains di(boroxyethylene tristyrylphenyl)methane as the compound, and methyl ethyl getoxime block of 4.4′-diphenylmethane diisocyanate as the blocked polyisocyanate compound containing polyacrylic acid alkyl ester partially hydrolyzed ammonium, 2,4.7.9-tetramethyl-5
An aqueous liquid containing monodecyne-4,7-diol (hereinafter referred to as aqueous liquid ①) was obtained in the following manner.

19 parts by weight of di<bolyoxyethylene tristyrylphenyl>methane (x=28, y=o in the [■] formula), 2
, 1 part by weight of 4.7.9-tetramethyl-5-decyne-4,7-diol, 2 parts of methyl ethyl ketoxime block of 4,4°-diphenylmethane diisocyanate.
00 parts by weight and 743 parts by weight of water were charged into a ball mill.
After treatment at 20 rpm for 36 hours, 28.5 parts by weight of a 20% by weight aqueous solution of partially hydrolyzed ammonium of butyl polyacrylate (degree of polymerization 3000) was added to 760 parts by weight of the liquid extracted from the ball mill and stirred for 1 hour.

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

Further, an RFL aqueous liquid was obtained in the following manner.

To a mixture of 396.6 parts by weight of water and 5.0 parts by weight of a 1% NaOH aqueous solution, 18.5 parts by weight of resorcin was added and dissolved, and further 27.2 parts by weight of a 37% formalin aqueous solution was added and mixed. After being incubated at ℃ for 8 hours, Nitzball 2518FS, which is a 40% by weight latex of vinylpyridine-styrene-butadiene copolymer (278.8 parts by weight, manufactured by Hiki Zeon Co., Ltd.) and 40% latex by weight of a styrene-butadiene copolymer. 142.0 parts by weight of Nipponore LX-110 (manufactured by Nippon Zeon Co., Ltd.) was added, and the mixture was aged at 25° C. for 16 hours.

Next, the first treatment liquid was prepared as follows.

140 parts by weight of aqueous liquid ■, 235 M parts of aqueous liquid ■, R
585 parts by weight of the FL aqueous liquid and 185 parts by weight of water were mixed and thoroughly stirred.

Further, a second treatment liquid was prepared as follows.

45 parts by weight of aqueous liquid ■, 455 parts by weight of RFL aqueous liquid,
400 parts by weight of water was mixed and thoroughly stirred.

On the other hand, a 6,000 denier polyethylene terephthalate chip having an intrinsic viscosity of 1.00 as measured at 20°C was melt-spun through a spindle with 288 holes in a mixed solvent of phenol/tetrachloroethane (1/1 weight ratio). A spinning oil containing a fatty acid ester and a nonionic surfactant as the main components is applied to the undrawn yarn using an oiling roller, and the yarn is stretched four times using a hot-rolling pin at 80°C and a slit heater at 170°C, and heat treated at the same time. A drawn yarn of 1500 denier was obtained.The two drawn yarns thus obtained were twisted 40 times/10 cm each in the bottom twist and the top twist to form a cord.

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. The cord thus applied and heat-treated with the first treatment liquid was immersed in the second treatment liquid, dried at 130°C for 2 minutes, and then heat-treated at 250°C for 90 seconds. The adhesive application rate to the cord was 3.8% by weight in the first treatment and 3.8% by weight in the second treatment based on the dry solid content of the untreated cord.
The treatment amount was 1.1% by weight. Table 1 shows the adhesive adhesion unevenness and performance evaluation results of the adhesive-treated cord thus obtained, as well as the foaming properties of the first treatment liquid. The composition of the rubber compound used to measure the T-initial adhesive strength and the fatigue resistance in rubber is shown below.

Natural rubber (RSS#1) 70 (parts by weight) SB
R (JRS1501) 30 ( )l
) SRF carbon black 40 (//) stearic acid 2<11> sulfur
2 (〃) Zinc white
5(〃)2,2゛-dithiobenzothiazole 2()l>Naphthenic acid process oil 3(〃
) For comparison, di(
Polyoxyethylene/tristyrylphenyl>methane (
[■] x in the formula = 28.37 = O) and 2.4, 7.9-
20 parts by weight of sodium naphthalene sulfonate was added instead of adding tetramethyl-5-decyne-4,7-diol (Comparative Example 1), and instead of adding the aqueous liquid ■ to the first treatment liquid of Example 1. In Comparative Example 2, 235 parts by weight of water was added to the mixture, and 200 parts by weight of water was added instead of adding the methyl ethyl ketoxime block of 4.4-1-diphenylmethane diisocyanate when preparing the aqueous solution (1) of Example 1. Comparative Example 3> In addition, when preparing aqueous liquid (1) of Example 1, water 28.
Same as Example 1 except that 5 parts by weight was added (Comparative Example 4), and 200 parts by weight of water was added instead of adding RFL aqueous liquid when preparing the first treatment liquid (Comparative Example 5). Table 1 also shows the adhesive adhesion unevenness and performance evaluation results of the adhesive-treated cord obtained in 1.

Examples 2 to 11 Di(boroxyethylene tristyrylphenyl)methane ([■
] Instead of x = 28, y = 0) in the formula, di(bolyoxyethylene boroxypropylene tristyrylphenyl)methane (x = 18, y = 3 in the formula) was used. (Example 2), di(boroxyethylene monostyrylphenyl)methane (x=20, y=
Example 3 using o), 2,4,7,9-tetramethyl-5-decyne-4 contained in the aqueous liquid
, 7-diol, 2 parts by weight of an ethylene oxide adduct of 2,4,7.9-tetramethyl-5-decyne-4.7-diol (m+n=4 in the [■] formula) was used (Example 4), similarly using 3 parts by weight of ethylene oxide adduct of 2.4.7.9-tetramethyl-5-decyne-4.7-diol (m+n in the formula [■] = 10) (Example 5) ), similarly, ethylene oxide adduct of 2.4.7.9-tetramethyl-5-decyne-4.7-diol (m+n=30>4 parts by weight in the [■] formula was used (Example 6) , Partially hydrolyzed ammonium of polymethyl acrylate was used instead of partially hydrolyzed ammonium of butyl polyacrylate contained in the aqueous solution (1) in Example 1 (Example 7), The blocked polyisocyanate compound in Solution (1) was replaced with an ε-caprolactam block of 4,4″-diphenylmethane diisocyanate (Example 8);
Similarly, 44--diphenylmethane diisocyanate was replaced with an ethyleneimine block (Example 9). The blocked polyisocyanate compound in the aqueous solution (1) added to the first treatment solution in Example 1 was changed to an ethyleneimine block of 4.4-1-diphenylmethane diisocyanate, and the second treatment solution was the same as in Example 1. (Example 10). 4. The blocked polyisocyanate compound in the aqueous solution (1) added to the second treatment solution in Example 1.
An adhesive treated cord obtained in the same manner as in Example 1 except for Example 11) except that the ethyleneimine block of 4-1 diphenylmethane diisocyanate was used and the first treatment liquid was the same as in Example 1. Adhesive adhesion unevenness, various performance evaluation results, and foaming properties of the first treatment liquid are also listed in Table 1.

As is clear from Table 2, the cord obtained by the method of the present invention has less uneven adhesive adhesion, flexibility, excellent fatigue resistance in rubber, and high and stable adhesive strength with rubber. It can be seen that this is an excellent method, as it is suitable for tire cords, and at the same time, there is little foaming of the first treatment liquid.

Examples 12-22, Comparative Examples 6-10 Example 1. ~1
The cords made of polyethylene terephthalate fibers in 1 and Comparative Examples 1 to 5 were replaced with the cords made of poly p-phenylene terephthalamide fibers ("Kevfar", manufactured by DuPont, 1500 denier, 1000 denier).
Adhesive processing cords obtained in the same manner as Examples 1 to 11 and Comparative Examples F to 5 except that the filaments were changed to 2 x 2 filaments, 40 first twists and 40 second twists (Example 1 corresponds to Example 12) , Example 2 corresponds to Example 13, Examples 3 to 11 correspond to Examples 14 to 22 in the same order, Comparative Example 1 corresponds to Comparative Example 6, and Comparative Example 2 corresponds to Examples 14 to 22, respectively. Evaluation results of adhesive adhesion unevenness and various performances and foaming of the first treatment liquid Gender is second
Shown in the table.

As is clear from Table 2, the cord obtained by the method of the present invention has less uneven adhesive adhesion, flexibility, excellent fatigue resistance in rubber, and high and stable adhesive strength with rubber. It can be seen that this is an excellent method, as it is suitable for tire cords, and at the same time, there is little foaming of the first treatment liquid.

Table I (Margin below)

Claims (1)

[Claims] A fiber material is treated with a first treatment liquid containing the following compounds (A) to (F), then heat-treated, and then treated with the following compounds (B) and (D). A method for treating a fiber material for reinforcing rubber, the method comprising treating with a second treatment liquid containing a heat treatment. (A) Compound represented by the following general formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [I] (However, x in the above [I] formula is an integer from 10 to 60, y
represents an integer of 0 to 60, and n represents an integer of 1 to 3. ) (B) Blocked polyisocyanate compound (C) Polyepoxide compound (D) Mixture of resorcinol/formalin resin and rubber latex (E) Partially hydrolyzed ammonium of polyacrylic acid alkyl ester (F) In the following general formula [II] Compound shown▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] (However, m and n in the above [II] formula are each 0 to 30.
)