JPS6055633B2 - Method for producing polyester fiber material with improved adhesion to rubber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polyester fiber material for rubber reinforcement that has improved adhesion to rubber compounds, especially when exposed to high temperatures for a long time while embedded in a rubber compound. The present invention relates to a method for producing a polyester fiber material for rubber reinforcement with significantly improved strength reduction.

Despite having excellent properties such as high tensile strength, heat resistance, fatigue resistance, and dimensional stability, polyester fibers (typically polyethylene terephthalate) have been delayed in practical application because they have difficulty adhering to rubber. ), the adhesion with rubber has improved through the development of adhesive treatment methods using adhesives such as epoxy resins, isocyanate resins, ethyneurea resins, and chlorophenol resins/resins, and today they are used in automobile tires, hoses, and belts. It has come to be widely used as a reinforcing material for rubber products such as rubber products. However, conventionally known adhesive-treated polyester fibers have the disadvantage that their adhesive strength with rubber compounds decreases significantly when they are exposed to high temperatures for long periods of time in rubber compounds. Usage conditions and applications are limited.

It is said that the cause of this decrease in adhesive strength in rubber compounds is the deterioration of polyester fibers due to the action of amines and moisture in the rubber compound. proposals have been made.

For example, chlortriazine compounds (French Patent No. 2066198), isatoic anhydride (Japanese Patent Publication No. 36276/1983), quicklime (Japanese Patent Publication No. 36276/1983), and
7-29471), etc., to block the action of amines and moisture in the comb, and methods using polyester fibers that are less susceptible to deterioration by reducing the amount of carboxyl terminal groups (Japanese Patent Publication No. 44-27911, Japanese Unexamined Patent Publication 1986-1970
No. 394), etc. have been proposed. However, the method of adding these chemicals into rubber compounds causes undesirable drawbacks such as blooming and deterioration of the physical properties of vulcanized rubber, and the method of using polyester fibers with a low amount of carboxyl end groups is difficult to use because of the presence of polar groups and functional groups. Since polyester fibers with fewer groups are made more non-polarized and have lower functional groups, they have the disadvantage that adhesion to rubber becomes more difficult, and it must be said that all of these proposals are of little practical use. I don't get it. Furthermore, JP-A-51-70394 proposes a method in which polyester fibers having a carboxyl terminal group content of 10 eq/1 Cf3y or less are subjected to epoxy compound treatment, polyisocyanate compound treatment, and resorcinol-formalin-rubber latex treatment. It is not practical because the polyisocyanate treatment is carried out using an organic solvent and is a three-stage dipping treatment. The present inventors have already published Japanese Patent Publication No. 47-49768 and Tamoto Patent No. 69276@)
In this process, polyester fibers are treated with epoxy in the form of yarn before or after drawing, and then subjected to protected isolysis in a subsequent step. We proposed that rubber-reinforcing polyester fibers with excellent adhesive strength and adhesive fatigue resistance during high-temperature vulcanization can be obtained by treating with a resorcinol-formalin-rubber latex mixture containing an anate group or/and an ethylene urea compound. However, as a result of further investigation, we found that polyester fibers that have been treated with a treatment solution containing an epoxy compound during the spinning or drawing process and then heat-treated are treated with protected isocyanate or/and ethylene urea compound and 4-resorcinol. By applying a two-step adhesive treatment in combination with a formalin-rubber latex mixture (hereinafter abbreviated as RFla), the decrease in adhesive strength when exposed to high temperatures for a long time in rubber was further significantly improved. The inventors have discovered that a polyester fiber material can be obtained, leading to the present invention. That is, the present invention does not require the use of polyester fibers having a particularly low amount of carboxyl end groups, and even when applied to a rubber compound with a composition commonly used for automobile tires, etc. A method for producing a polyester fiber material that has significantly improved adhesive strength reduction when exposed for a long time, in which polyethylene terephthalate fibers, which are commonly used as polyester fibers for rubber reinforcement, are processed in a spinning or drawing process. After treatment with a treatment liquid containing an epoxy compound having 1 or more epoxy groups, a yarn obtained by heat treatment at 150 to 260°C, a cord made by twisting the yarn, or a fabric woven from the yarn is treated with (4) After the first stage adhesive treatment with an aqueous dispersion of blocked isocyanate or/and ethylene urea compound or (B) RFL liquid containing blocked isocyanate or/and ethylene urea compound, further (C)
By treating the RFL liquid or (2) the RFL liquid containing blocked isocyanate or/and ethylene urea compound in the second stage, the adhesive property with rubber can be improved, especially when exposed to high temperatures for a long time in rubber. This is a method for obtaining a polyester fiber material for rubber reinforcement, which has significantly improved adhesive strength. The invention essentially consists of two components.
The first is to process melt-spun polyester fibers in the spinning or drawing process, that is, to treat polyester fibers that have not yet been sufficiently drawn to a treatment containing an epoxy compound having two or more epoxy groups. After treatment with liquid,
The second step is to heat-treat at 150 to 26σC, and the second step is to apply an aqueous dispersion of blocked isocyanate or/and ethylene urea compound to the polyester fiber yarn thus obtained, a cord made by twisting the same, or a fabric made from the same. and RFL liquid to perform a two-step adhesive treatment. The effects of the present invention can only be obtained when the above two requirements are combined. The second component of the present invention, which is a two-step adhesive treatment in which an aqueous dispersion of a blocked isocyanate or/and ethylene urea compound and an RFL liquid are combined, is explained below. an aqueous dispersion of R
Compared to the case of one-step adhesive treatment using a liquid mixture with FL (for example, the above-mentioned Japanese Patent Publication No. 47-49768), the two-step adhesive treatment of the present invention provides a much better improvement effect. . The reason is that blocked isocyanates and/or ethylene urea compounds are more effective adhesives than RFL for polyester fibers as adhesives located between the polyester fiber material and the rubber compound. On the other hand, RFL is considered to be a more effective adhesive for rubber compounds, so the first stage is based on blocked isocyanate or/and ethylene urea compound, and the second stage is based on RFL. This is because the composition can be appropriately selected based on. The present invention will be explained in more detail below.

The polyester fiber of the present invention is a fiber obtained by melt-spinning polyethylene terephthalate or a high molecular weight linear polyester mainly composed of ethylene terephthalate units, and has an intrinsic viscosity (in a mixed solvent of 3:2 of phenol, nitrate, and chlorethane). (measured at 30℃) is usually 0.6
5 or more, and the amount of carboxyl terminal groups is 35 eq/lσ
v or less, usually 15 to 3(t)q/ICF'y.

The melt-spun polyester fibers are usually subjected to drawing, twisting, weaving, and adhesive treatment, and are used, for example, as reinforcing materials for rubber products such as automobile tires. The first aspect of the present invention
The constituent requirement is that the melt-spun polyester fiber is treated with a treatment liquid containing an epoxy compound in the spinning or drawing process, and then heat-treated at 150 to 260°C.

The treatment with the treatment solution containing the epoxy compound is essential to be carried out in the spinning or drawing process, and the treatment of the yarn after drawing, the cord after twisting, or the fabric after weaving is not applicable to the present invention. does not achieve its purpose. Although the reason for this is not clear, it is thought that the epoxy compound is more firmly bonded to the polyester fiber in the unstretched state where the degree of orientation of the polyester molecular chains is low than in the highly oriented state after stretching. Further, even if the blocked isocyanate or/and ethylene urea compound-RFL adhesive treatment of the present invention is applied to ordinary polyester fibers that are not treated with a treatment solution containing an epoxy compound in the spinning or drawing process, the object of the present invention will not be achieved at all. . To treat with a treatment liquid containing an epoxy compound in the spinning or drawing process, for example, the epoxy compound is emulsified and dispersed in a spinning oil, and this is applied to the polyester yarn spun from a spinneret using an oiling roller in a conventional manner. For example, a treatment solution containing an epoxy compound may be applied to an undrawn yarn that has been treated with a conventional oil agent without an epoxy compound by a dipping method or a roller method at the introduction of the drawing step. After applying,
There are methods such as stretching.

A processing liquid containing such an epoxy compound contains a curing agent,
Compounds such as stabilizers and adhesion aids, for example, the present inventors disclosed in Japanese Patent Publication No. 47-44345 (Japanese Patent No. 7485W)
and Special Publication No. 48-41451 (Japanese Patent No. 7319
Compounds such as a thiourea compound, a mercaptobenzimidazole compound, or a polyester resin proposed in No. 81) may be added. 150-260C after being treated with a treatment liquid containing an epoxy compound in the spinning or stretching process
After the stretching process, the heat treatment may be carried out using, for example, a slit heater, an open or heated roller, but the stretching is generally carried out on a stretching pin, hot plate, roller, etc. heated to 80 to 260°C. Therefore, this stretching step can also serve as the heat treatment.

The epoxy compound used in the present invention has two or more epoxy groups in its molecule, and preferred examples include glycerin, propylene glycol, ethylene glycol, hexanetriol, sorbitol, melimethylolpropane, Reaction products of aliphatic polyhydric alcohols such as 3-methylpentanetriol, polyethylene glycol, polypropylene glycol and halohydrin such as epichlorohydrin, resorcinol, catechol,
Hydroquinone, 1,3,5,monotrihydroxybenzene, bis(4-hydroxyphenyl)methane, bis(4
- reaction products of aromatic polyhydric alcohols such as -hydroxyphenyl)dimethylmethane and 4,4''-pihydroxyphenyl with halohydrins such as epichlorohydrin;
Diglycidyl ether, vinylcyclohexene diepoxide, 3,4-epoxy-6-methylcyclohexylmethyl-3'',4''-epoxy 6''-methylcyclohexenecarboxylate, etc., obtained by oxidizing the unsaturated bond with peracetic acid, etc. Examples include epoxy compounds, and di- and triepoxides such as glycerin and 3-methylpentanetriol are particularly preferred.

The amount of the epoxy compound attached to the polyester fiber is 0.1 to 2. Saliva volume % is preferred. The polyester drawn yarn treated with a treatment solution containing an epoxy compound and heat-treated at 150 to 26 Cf'C, or a cord made by twisting the same in a conventional manner, or a fabric woven from the cord, is then processed into a main body. Adhesive treatment, which is the second component of the invention,
That is, after performing the first stage treatment with (4) an aqueous dispersion of a blocked isocyanate or/and an ethylene urea compound or (B) an RFL liquid containing a blocked isocyanate or/and an ethylene urea compound, then (C )
A two-stage adhesive treatment is performed in which a second stage treatment is performed with an RFL liquid or (2) an RFL liquid containing a blocked isocyanate or/and an ethylene urea compound. The adhesive treatment here refers to adhesive treatment liquid (A, B, C or D).
is applied to the fiber material by a conventional method such as spraying, impregnating, or coating, and then heat-treated by a conventional method such as passing through hot air.
It is preferable to carry out 1 to 1 times in 1 to 1 times.

In the case of the present invention, which is a two-step adhesive treatment, the above adhesive application step and subsequent heat treatment step are repeated twice.

The blocked isocyanate of the present invention includes, for example, tolylene diisocyanate, bitolylene diisocyanate,
Dianisidine diisocyanate, -tetramethylene diisocyanate, hexamethylene diisocyanate, m-phenylene diisocyanate, m-xylene diisocyanate, alkylbenzene diisocyanate, 1-chlorobenzene-2,4,-diisocyanate, cyclohexychlormethane diisocyanate, 3,3''-dimethoxydiphenylmethane- 4,4″-diisocyanate, 1-
Nitrobenzene-2,4-diisocyanate group, 1-alkoxybenzene-2,4-diisocyanate, ethylene diisocyanate, propylene diisocyanate,
Cyclohexylene-1,2-diisocyanate, 3,3
"-dichloro-4,4-biphenylene diisocyanate, diphenylene diisocyanate, 2-chlorotrimethylene di)isocyanate, butylene-1,2-diisocyanate, ethylidene diisocyanate, diphenylmethane-4,4"-diisocyanate, diphenylethane diisocyanate, 1 , 5 naphthalene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate 1, etc., triphenylmethane triisocyanate, diphenylmethane triisocyanate, butane-1,2,2-triisocyanate, trimethylolpropane tolylene diisocyanate 3 addition triisocyanates such as 2,4,4-diphenyl ether triisocyanate, polymethylene polyphenylisocyanate (crude diphenyl phenol, thiophenol, cresol, resorcinol, t-butanol, t-butanol, t-butanol, etc. Tertiary alcohols such as pentanol and t-butanethiol, aromatic amines such as diphenylamine, diphenylnaphthylamine, and xylidine, imides such as succinimide and phthalic acid imide, acetoacetate, acetylacetone, malonic acid diester, etc. active methylene compound, 2-mercaptobenzothiazole,
Mercaptans such as t-dodecyl mercaptan, lactams such as E-caprolactam, δ-valerolactam, γ-butyrolactam, β-proviolactam, ureas such as urea, diethylene urea, thiourea, acetoxime, cyclohexanone oxime, benzo Oximes such as phenone oxime and methyl ethyl ketone oxime, diaryl compounds such as carbazole, phenol naphthylamine, and N-phenylxylidine, bisulfites, boric acids,
It is obtained by reacting one or more isocyanate blocking agents such as α-pyrrolidone by a known method.

Among them, particularly preferred protected isocyanates are:
The isocyanate component is a polyisocyanate that at least partially contains molecules having three or more isocyanate groups, such as isocyanates such as triphenylmethane triisocyanate and trimethylolpropane tolylene diisocyanate teradduct; Examples include those obtained by blocking polyfunctional polyisocyanates such as polymethylene polyphenylisocyanate with the blocking agent described above. Although it is not clear why a block of polyisocyanate containing at least a portion of molecules having three or more isocyanate groups is particularly preferable, after the blocking agent dissociates, the polyisocyanate molecules having three or more functional groups It is believed that the formation of a dimensional network structure is effective in improving the heat resistance of adhesive strength.

More preferred among the particularly preferred blocked isocyanates are those in which the blocking agent is the lactams or oximes listed above, for example, triphenylmethane triisocyanate or polymethylene polyphenylisocyanate is combined with ε-caprolactam. Examples include those blocked with methyl ethyl ketone oxime.

Lactams and oximes are particularly preferred as blocking agents because the dissociation temperature of these blocking agents is close to the heat treatment temperature during adhesive treatment and because they cause less damage to the polyester after dissociation. I think that the.
The ethylene urea compound of the present invention includes, for example, monoisocyanates such as phenyl isocyanate, n-butyl isocyanate, and p-chloroisocyanate, diisocyanates, triisocyanates, and polymethylene polyphenyl as exemplified in the above protected isocyanate example. It is obtained by reacting polyfunctional isocyanates such as isocyanate with ethyleneimine by a known method, and among them, polyisocyanate and ethyleneimine which at least partially contain molecules having two or more isocyanate groups are used. For example, diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, triisocyanates such as triphenylmethane triisocyanate, trimethylolpropane tolylene diisocyanate teradduct, polymethylene poly Particularly preferred are reaction products of polyfunctional polyisocyanates such as phenyl isocyanate and ethyleneimine.

It is not clear why reaction products of polyisocyanates and ethyleneimine, which at least partially contain molecules with two or more isocyanate groups, are particularly preferred, but they are suitable for complex reactions of molecules with two or more imine groups. As a result, a three-dimensional network structure is formed, which is thought to improve the heat resistance of the adhesive force.

The RFL liquid used in the present invention includes an initial condensate obtained by reacting resorcin and formalin under an acid or alkali catalyst, styrene-butadiene latex, carboxyl group-containing styrene-butadiene latex, and styrene-butadiene-vinylpyridine latex. It is an aqueous liquid mixed with one or more latexes such as Tux, acrylonitrile-butadiene latex, polychloroprene latex, polybutadiene latex, and natural rubber latex, and the molar ratio of resorcinol to formalin is 1:0.
The solid content ratio between the resorcinol-formalin initial condensate and the latex is preferably 5 to 1:4 by weight.
A range of 95 to 5(7)50 is preferred.

The adhesive treatment of the present invention is carried out in two stages, and the first stage treatment consists of an aqueous dispersion of the above-mentioned blocked isocyanate or/and ethylene urea compound or a blocked isocyanate and/or ethylene urea compound. Treat with RFL liquid containing urea compound.

When the first stage treatment is carried out with an aqueous dispersion of a blocked isocyanate and/or an ethylene urea compound, the mixing ratio of the blocked isocyanate to the ethylene urea compound is 10(7) in solid weight ratio. 0 to 0 to 10
Using an aqueous dispersion with an effective concentration of blocked isocyanate or/and ethylene urea compound of 1 to 2% by heel weight, the amount deposited on the polyester fiber material is 0.0% on a dry weight basis. It is preferably 2 to 10%. Further, the first stage treatment includes R containing a blocked isocyanate or/and an ethylene urea compound.
In the case of using FL solution, the mixing ratio of blocked isocyanate to ethylene urea compound can be arbitrarily selected in the range of 100:0 to 0:100, and the mixed ratio of blocked isocyanate or/and ethylene urea compound to RF
The mixing ratio of L is 10(7)0 to 5:9 in solid weight ratio.
It is preferably in the range of 100:0 to 6(7)4, more preferably 5s. If the mixing ratio of blocked isocyanate and/or ethylene urea compound to FRL is less than 5:95, the effect of improving adhesion is insufficient. The adhesion amount of the mixed adhesive of blocked isocyanate or/and ethylene urea compound and RFL to the polyester fiber material is 0.2 to 10 on a dry weight basis.
% is preferable. The second stage treatment is performed using the RFL liquid described above or the RFL liquid containing blocked isocyanate or/and ethylene urea compound.

The amount of the second-stage treatment agent applied to the polyester fiber material is preferably 0.5 to 10% by dry weight. When the second stage treatment is performed with an RFL liquid containing a blocked isocyanate and/or an ethylene urea compound, the mixing ratio of the blocked isocyanate to the ethylene urea compound may be any value in the range of 100:0 to 0:100. The mixing ratio of blocked isocyanate or/and ethylene urea compound to RFL can be selected from O to 100 to 8 (7) 2, more preferably from 0 to 100 to 4 (7) 6 by solids weight. It is preferable that it is in the range of .
When the amount of blocked isocyanate and/or ethylene urea compound is more than 8(7)20 relative to RFL, the affinity with the rubber compound is low and sufficient initial adhesive strength cannot be obtained. In addition, the blocked isocyanate of the present invention or/
For example, the aqueous dispersion of the ethylene urea compound can be prepared by a conventional method such as ball milling, using the above-mentioned blocked isocyanate and/or ethylene urea compound with auxiliary agents such as a surfactant, a thickener, and an antifoaming agent. Adjust by dispersing in water.

The thus obtained polyester fiber material of the present invention has significantly improved adhesive strength reduction when exposed to high temperature for a long time in rubber compared to conventional polyester fiber materials, and therefore requires vulcanization at high temperature and for a long time. This is an epoch-making product that can also be applied to reinforcing materials for rubber products such as large tires and belts used under harsh conditions. The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

In addition, parts in the examples mean parts by weight. Example 1 Kohon 812 (manufactured by Shell Chemical Co., Ltd., glycerin, epichlorohydrin and reaction product) 30f
f/1 was dispersed to prepare an epoxy compound-containing spinning oil treatment solution.

On the other hand, a poly-ethylene terephthalate chip with an intrinsic viscosity of 1.03 (measured with 3CfC in a mixed solvent of 3:2 of ferrelnitetrachlorej tanni) was spun at a spinning temperature of 305°C with a pore diameter of 0.4TI$11 and a number of holes of 192. 250y/ from the base
Melt spinning is performed at a discharge rate of Min, and the undrawn yarn thus obtained is cooled to a temperature below the secondary transition point of the polymer, and then the above-mentioned epoxy compound-containing spinning oil treatment liquid is applied using an oiling roller as in a conventional method. 380 tiles/Min
It was wound at a speed of

Adhesion rate of epoxy compound is 0.8% based on yarn weight
It was hot. The undrawn yarn thus obtained by epoxy treatment was then drawn in two stages to a total of 6 times using a heating drawing pin at 990°C and a slit heater at 200°C.
Fixed length heat setting was performed on a 500C slit heater.
The residence time in the slit heater was 2j seconds for both stretching and heat setting. 1000d I got here
/192 filament polyethylene terephthalate drawn yarn has a carboxyl terminal group content of 18eq/1Cf'
V, and the intrinsic viscosity was 0.85 (measured by the above measuring method). Three of these yarns are twisted together to form one cord (
The number of twists x 41.5 T/1 h) was obtained. The code obtained in this way was converted into polymethylene polyphenylisocyanate (
ε of Millionate MR) manufactured by Nippon Polyurethane Industry Co., Ltd.
A 20% aqueous dispersion of one caprolactam block (this consists of 0.6 parts of methyl cellulose, 0.3 parts of sodium alkyl sulfonate, 0.1 part of polyethylene glycol monolaurylate and E-caprolactam blocked polymethylene polypropylene in one part of water). It was prepared by adding 2 parts of enyl isocyanate and crushing and dispersing it in a ball mill for 2 hours.) 30
The fish was immersed for 5 seconds in the first stage treatment solution diluted with 10 parts of water, and then heat-treated for 9 hours in heated air at 220°C.

The processing code obtained in this way is then used as the second stage processing liquid, RFL liquid (this is made by mixing 5J parts of resorcinol, 6.3 parts of 37% formalin aqueous solution, and 3 parts of 10% caustic soda aqueous solution with 185.7 parts of water). After heating at 30'C for 6 hours, 175.7 parts of Nitzpol 2518F'S [butadiene-styrene-vinylpyridine copolymer latex (solid content 41%) manufactured by Nippon Zeon Co., Ltd.] and 23.6 parts of water were added. (added) for 5 seconds. The fish were soaked for 9 hours, and then heat-treated for 9 hours in heated air at 220°C. The adhesive adhesion rate of the cord treated with two-stage adhesive in this way is that the first stage adhesive is 3.0% and the second stage adhesive is 3.0% based on the weight of the polyester cord.
The first stage adhesive was 2.1%.

The thus obtained two-stage adhesive treated cord was vulcanized and bonded with the following rubber compound at 140°C or 170°C for 60 minutes, and the H-adhesion strength was measured. The results are shown in Table 1. .

Rubber compound composition used in the adhesion test Smoked sheet No. 37O. Produced SBR-171242 - Produced zinc white 5' parts sulfur
2.5 parts stearic acid
2.5 parts N-cyclohexyl 2
-Benzothiazole sulfenamide (accelerator)
1” part pine tar 5.
0W) N-phenyl-N'-isopropyl-P-phenylenediamine (anti-aging agent) 1.5 parts FEF carbon black 5. For comparison, Table 1 shows Comparative Example 1, which was treated under the same conditions as Example 1, except that Kohon 812 was not added to the spinning oil treatment solution, and Kohon 812 was added to the spinning oil treatment solution. Comparative Example 2 was treated under the same conditions as Example 1, except that instead of adding the cord, the cord was twisted with a 5% aqueous solution of 812 and then heat-treated in heated air at 220°C for 908 minutes.
Instead of the two-step adhesive treatment of Example 1, the ε-caprolactam protected polymethylene polyphenylisocyanate 20% aqueous dispersion of Example 1 and the RFL liquid (total solids concentration 2) were used.
0%) and a treatment solution mixed in a ratio of 3 (7) 20.
Comparative Example 3 and Example 1-2 were treated under the same conditions as Example 1 except that the adhesive adhesion rate was 5.5% by weight based on the polyester cord. Comparative Example 4 is a case where the process is carried out under the same conditions as Example 1, except that the first stage treatment is not performed, and a case where the process is carried out under the same conditions as Example 1, except that the first stage process of Example 1 is not performed. Each is shown in Example 5.

As is clear from Table 1, the coat treated according to the invention (Example 1) gave better adhesion performance than any of Comparative Examples 1 to 5, especially when treated at 170°C. The adhesive strength was extremely high during high-temperature, long-term vulcanization, such as when vulcanizing.

Example 2 Everything is the same as Example 1 except that a reaction product of 4,4''-diphenylmethane diisocyanate and ethyleneimine (ethylene urea compound) is used in place of the ε-caprolactam-blocked polymethylene polyphenyl isocyanate of Example 1. After processing under the following conditions, the adhesive adhesion rates of the first and second stages were each 2% relative to the weight of the polyester cord.
．． Two stage adhesive treatment codes were obtained which were 8% and 2.1%.

The treated cord was heated at 140°C with the rubber compound of Example 1.
The H-adhesion strength when 4 powders or vulcanized at 170℃ for 60 minutes is 17.6k91cff1 and 12.8k91, respectively.
C1r1, and showed high initial adhesive strength and high heat-resistant adhesive strength. Example 3 Instead of the ε-caprolactam blocked polymethylene polyphenyl isocyanate of Example 1,
Except for using a 1:1 (weight ratio) mixture of a methyl ethyl ketone oxime block of triphenylmethane-4,4'',4''-triisocyanate and an ethyleneimine adduct (ethylene urea compound) of polymethylene polyphenylisocyanate. A cord treated under the same conditions as Example J1 (the adhesive adhesion rates of the first and second stages were 2. heel weight % and 2. heel weight %, respectively, with respect to the polyester cord) was used as an example. When 4 powders were vulcanized and bonded together with rubber compound No. 1 at 140°C or 6 powders at 170°C, the H-adhesion strength was 1 & 2k91 cm., respectively. The weight was 1,513.5 kg/at, demonstrating excellent initial mounting strength and heat-resistant adhesive strength.

Example 4 Hiren MP (manufactured by DuPont, a phenol block of diphenylmethane diisocyanate) was used in place of the ξ-caprolactam-protected polymethylene polyphenyl isocyanate of Example 1, and as the second-stage adhesive treatment liquid. Instead of the RFL liquid, a 20% aqueous dispersion of m-cresol block of hexamethylene diisocyanate (
A two-stage dip treatment code was obtained by processing under the same conditions as in Example 1 except for using a mixed treatment solution of 10C)Tll, which was prepared in the same manner as in Example 1, and the RFL liquid 30% of Example 1. Obtained.

The adhesive adhesion rates of the treated cords were 2.5% and 2.5%, respectively, based on the weight of the polyester cord. When the treated cord was vulcanized and bonded with the rubber compound of Example 1 at 140°C, 4 times or 170°C, the H-adhesion strength was as follows:
They were 17.0k9g and 11.2kg'o, respectively, indicating high initial and heat-resistant adhesive strength. Example 5 After dissolving and dispersing 15CB of Kohon 812 in an aqueous emulsion obtained by dissolving 2 concave portions of a polyester fiber spinning oil containing a fatty acid ester and a nonionic activator in 90% of water, 15 parts of mercaptobenzimidazole to 9 parts of water
Spinning oil treatment solution containing epoxy compound and mercaptobenzimidazole is mixed with a dispersion prepared using part (1) of Nitsusanrapizole B-30 (anionic activator manufactured by Nissan Chemical Co., Ltd.) (1) part. adjusted.

Polyester fibers were spun and drawn under the same conditions as in Example 1, except that this treatment liquid was used in place of the spinning oil treatment liquid in Example 1. 1000d/192 obtained here
The amount of carboxyl terminal groups in the filament polyethylene terephthalate drawn yarn was 18 eq/103y, and the solid content of the spinning oil treatment solution containing the epoxy compound and mercaptobenzimidazole was 1.0% based on the weight of the yarn.

Three of these drawn yarns were twisted together to obtain one cord (number of twists x 41.5 T/10 cm). The thus obtained cord was used to prepare ε-caprolactam-blocked polymethylene polyphenylisocyanate 2 prepared in the same manner as in Example 1.
Ethylene imine adduct of 0% aqueous dispersion (1) part and diphenylmethane diisocyanate (ethylene urea compound)
It was immersed for 5 seconds in a mixed adhesive treatment solution in which a 20% aqueous dispersion 2 and RFlalOO was mixed, and then heat-treated in heated air at 220° C. for a second.

The adhesive adhesion rate was 4.2% based on the polyester cord. The first stage treatment cord was then treated with an ethyleneimine adduct of E-caprolactam blocked polymethylene polyphenyl isocyanate and diphenylmethane diisocyanate, which consisted of the same components as used in the first stage adhesive above. (ethylene urea compound) to RFL solid content mixing ratio of 8DW, 2 parts to 2 parts to 200 parts for 5 seconds in the second stage adhesive treatment solution, and then dented in heated air at 23 (s). Heat treated for seconds. The adhesive adhesion rate of the second stage was 2.296 with respect to the polyester cord.

Table 2 shows the H-adhesion strength when the thus obtained adhesive-treated cord was vulcanized and bonded with the rubber compound of Example 1 at 140°C and 4 powder or 170'Cl6 powder.

For comparison, Table 2 shows Kohon 812 in the spinning oil.
Comparative Example 6 was treated under the same conditions as Example 5 except that the dispersion of mercaptobenzimidazole and mercaptobenzimidazole was not added.
Instead of adding a dispersion of Kohon 812 and mercaptobenzimidazole in the spinning oil, after twisting into cords, 5 parts of Kohon 812 and 0.5 parts of mercaptobenzimidazole were mixed into 88.6 parts of water. Sanrapizole 5.
After immersion for 5 seconds in an aqueous dispersion using 9 parts of
Comparative Example 7 shows a case where the treatment was carried out under the same conditions as in Example 5 except that the heat treatment was carried out in heated air at 0° C. for 9 times. As is clear from Table 2, the cord obtained by treatment according to the present invention (Example 5) is superior to Comparative Example 6 or 7, which is not treated with a treatment solution containing an epoxy compound and mercaptobenzimidazole at the spinning stage. It showed extremely high initial adhesive strength and excellent heat-resistant adhesive strength.

Claims (1)

[Scope of Claims] 1. A yarn obtained by treating polyester fiber with a treatment liquid containing an epoxy compound having two or more epoxy groups in a spinning or drawing process and then heat-treating it at 150 to 260°C. A twisted cord or a fabric woven from the cord is mixed with resorcinol per solid content of 60 to 100 parts of blocked isocyanate or/and ethylene urea compound.
A polyester fiber material with improved adhesion to rubber, characterized in that it is treated with a mixed solution or aqueous dispersion containing formalin-rubber latex solid content of 40 to 0 parts, and then further treated with a resorcinol-formalin-rubber latex mixed solution. manufacturing method. 2 Final adhesive treatment liquid resorcinol formalin
The method for producing a polyester fiber material according to claim 1, wherein a blocked isocyanate or/and an ethylene urea compound is contained in the rubber latex mixture. 3. The method for producing a polyester fiber material according to claim 1 or 2, wherein the isocyanate component of the blocked isocyanate is a polyisocyanate that at least partially contains molecules having three or more isocyanate groups. 4. The method for producing a polyester fiber material according to claim 1, 2 or 3, wherein the blocking agent component of the blocked isocyanate is a lactam or an oxime. 5. The polyester fiber according to claim 1 or 2, wherein the ethylene urea compound is a reaction product of ethyleneimine and a polyisocyanate that at least partially contains molecules having two or more isocyanate groups. Manufacturing method.