JP2000234275A - Treatment of polyester fiber for rubber reinforcement - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain excellent adhesivity of a polyester fiber to a rubber compound even at high temperature by treating a polyester fiber with an adhesive treatment agent containing a compound having a vinyl halide group and treating the product with a liquid containing a resorcinol-formaldehyde-rubber latex, etc. SOLUTION: A polyester fiber is immersed in a treating liquid having a solid component concentration of 1-30% and containing a compound having a vinyl halide group and a film-forming temperature of <=200 deg.C such as polyvinyl chloride in an amount of 3-85 wt.% based on the solid component of the treating agent and further containing a polyepoxide compound and/or a blocked polyisocyanate and a rubber latex to apply the treating agent to the polyester fiber in an amount of 0.1-10%. The treated polyester fiber is immersed in a liquid having a solid component concentration of 1-30%, containing a blocked polyisocyanate compound and a resorcinol-formaldehyde-rubber latex and preferably incorporated with an aromatic epoxide to effect the application of the treating liquid in an amount of 0.1-10%. The product is dried and heat-treated to fix the agent to the fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a polyester fiber for rubber reinforcement, and more particularly, to a method for treating a polyester fiber for rubber reinforcement by treating the polyester fiber with a treating agent containing a compound containing a vinyl halide group. About.

[0002]

2. Description of the Related Art Polyester fibers represented by polyethylene terephthalate fibers have excellent physical properties such as high strength and high Young's modulus.
It is used as a fiber for reinforcing rubber such as hoses and belts. However, since the surface of the polyester fiber is relatively inert, the adhesiveness of the polyester fiber to a matrix such as rubber or resin is insufficient, and the physical properties of the polyester fiber cannot be sufficiently exhibited.

[0003] Therefore, a chemical treatment method for treating the surface of polyester fiber with various chemicals, for example, treatment with a highly reactive chemical such as an aliphatic epoxy compound or a blocked isocyanate compound to impart adhesiveness. A so-called two-bath treatment method for treating with resorcin-formalin rubber latex (RFL) has been proposed and put to practical use (for example, JP-A-54-73994). Further, in a system in which a blocked isocyanate and an aromatic epoxy compound are added to the RFL, Japanese Patent Application Laid-Open No. 10-46
As described in Japanese Patent No. 475, it is possible to perform treatment in one bath.

However, it is known that in these methods, when the polyester is heated to a high temperature in an atmosphere containing an amine, a catalytic molecular cleavage reaction (aminolysis) by the amine occurs, and the strength is greatly deteriorated. . Generally, rubber contains a large amount of amine components to prevent the deterioration of the rubber, and when the rubber reinforced with polyester fibers is exposed to high temperatures, the surface of the polyester fibers deteriorates, and the adhesive strength may significantly deteriorate. Are known. In particular, when the adhesion amount of the adhesive (SPU) is small, the deterioration is large. Therefore, a treatment method that reduces the adhesion amount of the adhesive and obtains high adhesiveness is desired.

On the other hand, as a bonding technique between polyester fiber and rubber using vinyl halide, for example, Japanese Patent Publication No.
As described in JP-A-6-5740, treatment with a first treatment liquid containing polyvinyl chloride and polyamine as main components,
Subsequently, there is a method of treating with a second treatment liquid containing a rubber latex dispersion, but in this method, the affinity of the first treatment liquid with the polyester fiber is insufficient, and the film strength of the second treatment liquid is insufficient. Since it is sufficient, sufficient adhesiveness cannot be obtained.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and proposes a processing method in which the bonding performance between a polyester fiber and a rubber compound is excellent even when exposed to high temperatures. Is to do.

[0007]

An object of the present invention is to treat a polyester fiber with a treating agent (1) containing a compound containing a vinyl halide group, a polyepoxide compound and / or a blocked polyisocyanate compound, and a rubber latex. After that, the problem is further solved by a two-bath treatment method of treating with a treating agent (2) containing a blocked polyisocyanate compound and resorcinol-formalin rubber latex. Further, the polyester fiber is treated with a compound containing a vinyl halide group having a film formation temperature of 200 ° C. or lower, an aromatic polyepoxide compound, and / or a blocked polyisocyanate compound, and a resorcinol / formalin / rubber latex ( The treatment may be performed by the one-bath treatment method described in 3).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyester fiber used in the present invention may be any polyester fiber.In particular, terephthalic acid or naphthalenedicarboxylic acid is used as a main acid component, and ethylene glycol or a polyester containing tetramethylene glycol as a main glycol component is used. Fibers are preferably used. The denier, the number of filaments, the cross-sectional shape, the fiber properties, the fine structure, the polymer properties (terminal carboxyl group concentration, molecular weight, etc.) of the polyester fiber, the presence or absence of additives in the polymer, and the like are not limited at all. Further, the polyester fiber referred to in the present invention includes various fiber aggregate forms such as yarn, cord, non-woven fabric, woven and knitted fabric.

In the present invention, it is important to treat such a polyester fiber with a treating agent containing a compound containing a vinyl halide group. The compound containing a vinyl halide group used in the present invention has a film-forming temperature of 200 ° C. or lower, more preferably 180 ° C. or lower. When the film formation temperature exceeds 200 ° C., it becomes difficult to form a uniform film under the conditions of the bonding treatment. As the compound containing a vinyl halide group used in the present invention, vinyl chloride alone or a compound obtained by performing various copolymerizations, vinyl chloride and vinyl acetate, vinyl chloride and vinylidene chloride, vinyl chloride and acrylonitrile And terpolymers of vinyl chloride, vinyl acetate and maleic anhydride, or mixtures thereof.

In the present invention, the compound containing a vinyl halide group is used as an aqueous dispersion, emulsion or solution. To make such an emulsion or dispersion,
For example, the thermoplastic resin, as it is, or
After dissolving in a small amount of solvent if necessary, a known emulsifier,
For example, emulsification or dispersion may be carried out using sodium alkylbenzene sulfonate, sodium salt of dioctyl sulfosuccinate, an adduct of nonylphenol ethylene oxide, or the like.

In the present invention, the treatment is carried out with a treating agent containing such a compound containing a vinyl halide group, and more specifically, a compound containing the vinyl halide group, a polyepoxide compound and / or a block. Treated with a treating agent (1) containing a polypolyisocyanate compound and rubber latex (first treatment), and further, after the first treatment, a blocked polyisocyanate compound,
A two-bath method of treating (second treatment) with a treating agent (2) containing resorcinol / formalin / rubber latex is exemplified, and the treating agent (2) may further contain an aromatic polyepoxide compound. .

When an aromatic polyepoxide compound is used as the polyepoxide compound, the compound containing a vinyl halide group, an aromatic polyepoxide compound and / or a blocked polyisocyanate compound, and resorcinol-formalin rubber It can be treated by a one-bath method of treating with a treating agent (3) containing latex. Further, after the treatment with the treating agent (3),
Further, the treatment can be carried out once or a plurality of times with the treatment agent (4) containing resorcinol / formalin / rubber latex.

The polyepoxide compound used in such a treating agent is a compound having at least two or more epoxy groups in one molecule, and the content of the epoxy group is as follows:
The polyepoxide compound is a compound containing 0.2 g equivalent or more per 100 g. Examples of such compounds include reaction products of polyhydric alcohols such as ethylene glycol, glycerol, sorbitol, pentaerythritol, and polyethylene glycol with halogen-containing epoxides such as epichlorohydrin, resorcinol, bis (4-hydroxyphenyl) dimethylmethane A phenol-formaldehyde resin, a reaction product of a polyhydric phenol such as resorcinol-formaldehyde resin and the halogen-containing epoxide, peracetic acid, or a polyepoxide compound obtained by oxidizing an unsaturated compound with hydrogen peroxide or the like, That is, 3,4-epoxycyclohexene epoxide, 3,4-epoxycyclohexylmethyl,
4-epoxycyclohexene carboxylate, bis (3,4-epoxy-6-methyl-cyclohexylmethyl) adipate and the like can be mentioned. Of these, a reaction product of a polyhydric alcohol and epichlorohydrin, that is, a polyglycidyl ether compound of a polyhydric alcohol is particularly preferred because it can exhibit excellent performance.

The polyepoxide compound is preferably used as an aqueous solution or an emulsion. Emulsified liquid, or, for example, a solution, such a polyepoxide compound as it is, or dissolved in a small amount of solvent as needed, known emulsifiers, for example, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate It can be emulsified or dissolved using a salt, a nonylphenol ethylene oxide adduct, or the like.

Next, the blocked polyisocyanate compound used in the treatment of the present invention is an addition compound of a polyisocyanate compound and a blocking agent, and the heating releases a blocking component to produce an active polyisocyanate compound. It is a thing to tighten.

The polyisocyanate compound includes, for example, polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, and the like. Terminal isocyanate group obtained by reacting a compound having two or more hydrogen atoms, for example, trimethylolpropane, pentaerythritol, or the like, at a molar ratio of isocyanate group (-NCO) to hydroxyl group (-OH) exceeding 1 Contained polyol adduct polyisocyanate. In particular, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenyl isocyanate are preferred because they exhibit excellent performance.

Examples of the blocking agent include phenols such as phenol, thiophenol, cresol and resorcin; aromatic secondary amines such as diphenylamine and xylidine; phthalimides; caprolactam;
Examples include lactams such as valerolactam, oximes such as acetoxime, methyl ethyl ketone oxime and cyclohexanone oxime, and sodium acid sulfite.

Such a blocked polyisocyanate compound is usually used as an emulsion, a dispersion, or an aqueous solution. Emulsion, or, to make a dispersion, for example, such a blocked polyisocyanate, as it is, or, if necessary, dissolved in a small amount of solvent,
What is necessary is just to emulsify or disperse | distribute using well-known emulsifiers, for example, sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol ethylene oxide adduct, etc.

The present invention relates to such a polyepoxide compound,
In addition, by using a blocked polyisocyanate compound in combination with a compound containing a vinyl halide group, the affinity for polyester fibers can be greatly improved, and the initial adhesiveness can be greatly improved.

The rubber latex used in the present invention includes, for example, natural rubber latex, styrene / butadiene copolymer latex, vinylpyridine / styrene / butadiene terpolymer latex, nitrile rubber latex, chlorobrene rubber latex and the like. ,
These may be used alone or in combination. Among them, those using vinylpyridine / styrene / butadiene terpolymer latex alone or in combination with others are preferred. When used in combination, excellent performance can be obtained when the vinylpyridine / styrene / butadiene terpolymer latex is used in an amount of 1/3 or more of the total weight of the latex.

Further, in the present invention, an aromatic polyepoxide compound can be used as the polyepoxide compound used in the treatment agent. Such an aromatic polyepoxide compound is a compound having at least one aromatic ring and at least two epoxy groups in the molecule among the above polyepoxide compounds, and the content of the epoxy group is 2 equivalents per 1 kg of the compound. Above, preferably 3-7
The equivalent is particularly preferably in the range of 4 to 5 equivalents. When the polyepoxide compound is aliphatic, the reactivity with the resorcinol-formalin rubber latex (RFL) solution described below is too high, and the treating agent gels during the treatment of the polyester fiber, and the resulting adhesive performance is poor. It is not preferable because it decreases when the time passes after the treatment agent adjustment.

Specific examples of such an aromatic polyepoxide compound include a reaction product of a polyhydric phenol and a halogen-containing epoxide such as epichlorohydrin, for example, resorcin, bis (p-hydroxyphenyl) methane, 1,1 Reaction products of 2,2,2-tetrakis (p-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) dimethylmethane, phenol / formaldehyde resin, cresol / formaldehyde resin, resorcin / formaldehyde resin, etc. with epichlorohydrin;
An aromatic epoxy resin, which is a reaction product of bisphenol A and epichlorohydrin, and the like can be given. Of these, glycidyl ethers of phenolic resins represented by the following formula are preferred.

[0023]

Embedded image

In the formula, X represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 5.

The aromatic polyepoxide compound is usually used as an emulsion or dispersion. In order to prepare an emulsion or a dispersion, for example, the aromatic polyepoxide compound as it is, or a solution obtained by dissolving it in a small amount of a solvent, if necessary, can be used as a known emulsifier, for example, sodium alkylbenzene sulfonate, dioctyl sulfoate. What is necessary is just to emulsify or disperse using succinate sodium salt, nonylphenol ethylene oxide adduct, etc.

The treating agent (1) used in the present invention comprises a compound (A) containing a vinyl halide group as described above, a polyepoxide compound (B), a blocked polyisocyanate compound (C), and a rubber latex ( L), the content of the vinyl halide group-containing compound (A) in the fixed component is in the range of 3 to 85% by weight, and the polyepoxide compound (B) and the blocked polyisocyanate Regarding the compounding weight ratio of each component of the compound (C) and the rubber latex (L), (B) /
{(B) + (C)} is 0.05 to 0.9, (L) /
It is preferable to use such that {(B) + (C)} is 0.2 to 10. In particular, the content of the compound (A) containing the vinyl halide group in the solid component is 5 to 8
0% by weight, (B) / {(B) + (C)} is 0.1 to 0.1%.
It is preferable that (L) / {(B) + (C)} be in the range of 0.5 to 8.

When the content of the vinyl halide group-containing compound (A) in the solid component is less than 3% by weight, the wettability to the polyester fiber surface is reduced and the adhesive film is not coated. When the fiber is embedded in rubber and exposed to a high temperature, the adhesiveness is reduced. When the content is more than 85% by weight, the film forming property is deteriorated, Adhesive strength is reduced due to the inability to alleviate the stress generated due to differences in deformation characteristics due to heat and chemical changes, and stress is concentrated on the interface due to various deformations of the fiber rubber composite, resulting in fatigue of adhesive strength. It is not preferable because the characteristics are deteriorated.

The above (B) / {(B) + (C)}
Is less than 0.05, the adhesion to the polyester fiber is reduced, and when (B) / {(B) + (C)} is more than 0.9, the treated polyester fiber becomes hard, It is not preferable because fatigue properties may be reduced.
When the ratio (L) / {(B) + (C)} is less than 0.2, the treated polyester fiber becomes hard, which may cause a decrease in fatigue resistance, and a treatment agent ( 2)
Co-vulcanization with the latex and rubber as the adherend becomes insufficient and the adhesiveness becomes low, while (L) / （(B) +
(C) When｝ exceeds 10, the affinity to the polyester fiber side becomes insufficient, so that the adhesiveness decreases, which is not preferable.

The treatment agent (1) containing the compound (A) containing a vinyl halide group, the polyepoxide compound (B), the blocked polyisocyanate compound (C) and the rubber latex (L) has a total solid content concentration of: , 1-30
%, Preferably 1.5 to 20% by weight, more preferably 2 to 15% by weight. If the total solid content is too low, the surface tension of the adhesive increases, and the uniform adhesion to the polyester fiber surface decreases, and the adhesion decreases due to the decrease in the amount of solids attached. If the concentration of the agent is too high, the solid content becomes too large, so that it becomes hard and the fatigue resistance is apt to decrease, which is not preferable.

When the composition of the treating agent (1) is used as an aqueous dispersion, an appropriate amount of the dispersing agent, that is, the surfactant, is 15% by weight based on the total solid content of the treating agent (1). %, Preferably 10% by weight or less. If the amount of the surfactant exceeds 15% by weight, the adhesiveness tends to slightly decrease.

The solid content of the treating agent (1) on the polyester fiber is preferably in the range of 0.1 to 10% by weight, more preferably 0.3 to 7% by weight.
And more preferably in the range of 0.5 to 3% by weight. In order to control the amount of solids adhering to the polyester fiber, means such as squeezing with a pressing roller, scraping off with a screver, blowing off with air blowing, suction, and beating with a beater may be employed. Also, it may be applied a plurality of times to increase the amount of adhesion.

In the present invention, after the treatment (first treatment) with the treatment agent (1), the treatment agent (2) further containing a blocked polyisocyanate compound and resorcinol-formalin rubber latex (RFL) 2) is a two-bath process in which the second process is performed.

The content of the blocked polyisocyanate compound in the treating agent (2) is 0.5 to 30% by weight, preferably 1.0 to 20% by weight, based on resorcinol / formalin / rubber latex (RFL). Is preferably in the range of If the amount is less than 0.5, good adhesive strength may not be obtained.
If the content exceeds 0% by weight, the viscosity of the adhesive is significantly increased, so that the fiber processing operation becomes difficult, and the fiber after the processing becomes extremely hard, and the strength and fatigue resistance may be reduced, which is not preferable.

The resorcinol-formalin rubber latex (RFL) used in the treating agent (2) has a molar ratio of resorcinol to formaldehyde of 1: 0.1 to 1:
Those in the range of 8 are used, more preferably 1:
0.5-1: 5, more preferably 1: 1
Used in the range of 1: 4. When the addition amount of the formaldehyde is too small, the crosslink density of the condensate of resorcinol formalin decreases and the molecular weight decreases, so that the adhesiveness may decrease due to a decrease in the cohesive force of the adhesive layer. If the amount of formaldehyde added is too large, the resorcinol formalin condensate becomes hard due to an increase in crosslink density, compatibilization between RFL and the rubber is inhibited during co-vulcanization with the adherend rubber, and the adhesiveness decreases and the It is not preferable because the fiber becomes extremely hard and the strength and fatigue properties are reduced.

Resorcinol in the treating agent (2)
The mixing ratio of formalin and rubber latex varies depending on the addition ratio of the blocked polyisocyanate compound, but the resorcinol-formalin:
A rubber latex (RFL) in a range of 1: 1 to 1:15 is used, and a rubber latex (RFL) in a range of 1: 3 to 1:12 is particularly preferably used. If the proportion of the rubber latex is too small, the treated polyester fiber becomes hard and the fatigue resistance tends to decrease, and the treating agent (1)
The co-vulcanization with the latex and the rubber as the adherend may be insufficient and the adhesiveness may be reduced. Conversely, if the ratio of the rubber latex is too large, sufficient strength is obtained as an adhesive film. Therefore, there is a possibility that a satisfactory adhesive strength and a rubber adhesion rate cannot be obtained.

The blocked polyisocyanate compound (C) in the treating agent (2) and resorcinol
Formulation weight ratio of each component of formalin: rubber latex (RFL): (C) / (RFL) is in the range of 4/6 to 1/9, particularly in the range of 5/5 to 2/8. Those are preferably used. When the compounding weight ratio is larger than the above range, the polyester fiber after treatment may be hardened and cause a decrease in fatigue resistance.On the other hand, when the compounding weight ratio is smaller than the above range, Adhesion tends to decrease.

As such a treating agent (2), those having a total solid content concentration in the range of 1 to 30% by weight are suitably used.
Preferably, it is used in the range of 5 to 20% by weight. If the concentration of the treating agent (2) is lower than the above range, the adhesion amount of the adhesive will be reduced, and the adhesiveness will be reduced. Conversely, if the concentration of the treating agent (2) is too high than the above range. Since the solid content becomes too large, the polyester fiber becomes hard and the fatigue resistance is apt to decrease, which is not preferable.

The treatment agent (2) can be attached to the polyester fiber by contact with a roller, application by spraying from a nozzle, or immersion in a solution. The solid content of the treating agent (2) with respect to the polyester fiber is preferably in the range of 0.1 to 10% by weight, preferably in the range of 0.2 to 7% by weight, and more preferably in the range of 0.2 to 7% by weight. , 0.5 to 3% by weight. In order to control the solid content adhesion amount to the polyester fiber, similarly to the treatment agent (1), the solid content can be controlled by means of squeezing with a pressing roller, scraping off with a screver, blowing off by air blowing, suction, and beater. .

Further, the treating agent (2) may contain an aromatic polyepoxide compound (D). In this case, the treating agent (2) comprises an aromatic polyepoxide compound (D), Polyisocyanate compound (C),
And resorcinol-formalin rubber latex (RF
L), and the treating agent (3) comprises:
As described above, the treating agent contains the compound (A) containing a vinyl halide group, the aromatic polyepoxide compound (D), the blocked polyisocyanate compound (C), and the resorcinol-formalin rubber latex (RFL).

When the aromatic polyepoxide compound (D) is thus contained, the blending weight ratio of each component is not more than (D) / (aromatic polyepoxide compound / D) / blocked polyisocyanate compound (C). The｝ described as in (C) is exemplified in the range of 8/2 to 1/9, particularly preferably in the range of 8/2 to 4/6. Also,
{(D) + (C)} / (RFL) is, for example, in the range of 4/6 to 1/9, and particularly preferably in the range of 5/5 to 2/8.

If the ratio of the aromatic polyepoxide compound (D) to the blocked polyisocyanate compound (C) is out of the above range, the rubber adhesion to polyester fibers tends to decrease, which is not preferable. Also, ｛(D) +
When (C)｝ / (RFL) is larger than the above range, the polyester fiber after treatment may be hardened and cause a decrease in fatigue resistance. On the other hand, when smaller than the above range, Adhesion tends to decrease, which is not preferable.

As described above, the aromatic polyepoxide compound (D), the blocked polyisocyanate compound (C),
And resorcinol-formalin rubber latex (RF
L) -containing treating agent (2) and treating agent (3)
Those having a total solid content in the range of 1 to 30% by weight are exemplified, and can be used preferably in a range of 2 to 25% by weight, more preferably 5 to 20% by weight. When the total solid content of the treating agent (2) and the treating agent (3) is lower than the above range, the surface tension of the adhesive increases, and the uniform adhesion to the polyester fiber surface decreases, and On the other hand, when the total solid content is higher than the above range, the solid content becomes too large, so that the solid content becomes too high, and the solid content becomes too high, resulting in fatigue resistance. Easily deteriorates.

The treatment agent (2) and the treatment agent (3) can be attached to the polyester fiber by contact with a roller or by spraying from a nozzle.
Alternatively, means such as immersion in a solution can be adopted. Further, the solid content adhesion amount to the polyester fiber is 0.1 to 1
A range of 0% by weight is exemplified, preferably a range of 0.2 to 7% by weight, and more preferably a range of 0.5 to 6% by weight. In order to control the solid content adhesion amount to the polyester fiber, similarly to the above, squeezing by a pressing roller, scraping off by a screver, blowing off by air blowing, suction, and beater means can be performed. In order to increase the number, it may be applied plural times.

In the present invention, after treating the polyester fiber with such a treating agent, the polyester fiber is dried and heat-treated at a temperature of 50 ° C. or more and lower than the melting point of the polyester fiber by 10 ° C. or more. More preferably, drying and heat treatment are performed in a temperature range of 220 to 250 ° C. for 0.5 to 5 minutes, preferably 1 to 3 minutes. If the drying / heat treatment temperature is too low, adhesion to rubbers tends to be insufficient, and
If the heat treatment temperature is too high, the strength of the polyester fiber is remarkably reduced due to melting and fusion of the polyester fiber, and the polyester fiber cannot be put to practical use.

[0045]

As described above, according to the present invention, a rubber reinforcing material having high adhesion performance is obtained by treating a polyester fiber with a treating agent (1) or a treating agent (3) containing a compound containing a vinyl halide group. Polyester fiber is obtained.

In particular, when the rubber latex is used in combination with a compound containing a vinyl halide group, the flexibility and toughness of the adhesive film are improved, and the deformation characteristics of the polyester fiber and rubber due to heat and chemical changes are observed. In the case where the generated stress based on the difference is reduced or a stress is applied from the outside, a function of effectively dispersing the force is provided, and higher adhesiveness can be obtained. Further, the rubber latex contained in the treating agent (1), the rubber latex contained in the RFL as the treating agent (2), and the rubber as the adherend are co-vulcanized, so that high rubber adhesion and high adhesion are obtained. Adhesiveness can be realized.

Further, the compound containing a vinyl halide group has a solubility parameter close to that of the polyester fiber and has a high affinity with the polyester at the time of dissolution, so that the adhesive can be uniformly applied to the surface of the polyester fiber. . Therefore, even when the concentration of the processing solution is reduced due to these chemical and physical properties, it is possible to form a good film without defects on the polyester fiber surface.
By forming a uniform film on the polyester fiber surface in this way, even when the fiber is embedded in rubber and exposed to high temperatures, the diffusion of amine contained in rubber to the polyester fiber surface is prevented, and the adhesive strength is improved. Can be prevented from deteriorating.

Further, when the treating agent (2) is a system containing an aromatic polyepoxide compound (D), a blocked polyisocyanate compound (C), and resorcinol-formalin rubber latex (RFL), only this is used. Adhesive to polyester fiber and rubber. Therefore, in the first treatment with the treatment agent (1), even when the amount of the treatment agent (1) attached is small and the polyester fiber surface is not completely covered with the treatment agent (1), the treatment agent (2) ) Is considered to provide excellent adhesion.

As described above, when a compound containing a vinyl halide group having good coatability is added to the treating agent (1), even when the amount of the adhesive adhered is small as compared with a system without the addition, The decrease in adhesion between the polyester fiber and the rubber compound when exposed to a high temperature can be reduced, and the performance is further improved by adding an aromatic polyepoxide compound to the treating agent (2).

Further, a polyester fiber is formed by converting a compound containing a vinyl halide group having a film formation temperature of 200 ° C. or less,
In the case of treating with an aromatic polyepoxide compound and / or a blocked polyisocyanate compound and a treating agent (3) containing a resorcinol / formalin / rubber latex, sufficient adhesion can be obtained even by a single bath method. Excellent adhesive performance between the polyester fiber and the rubber compound can be obtained even when exposed to high temperatures.

[0051]

The present invention will be described in more detail with reference to the following examples. In addition, the measurement of the characteristic in an Example was performed by the following measuring methods.

(1) The polyester cord after the high-strength bonding treatment is JIS L101
It measures according to the method of 3.

(2) Cord Peeling Adhesive Strength This shows the adhesive strength between the treated cord and rubber. Seven cords are buried near the surface layer of a carcass-containing unvulcanized rubber sheet containing natural rubber as a main component, and a pressing pressure of 50 kg / cm ² (initial value) at a temperature of 150 ° C. for 30 minutes, or
Vulcanized at a temperature of 180 ° C. for 60 minutes under a pressing pressure (heat resistance value) of 50 Kg / cm ² , and then left five cords in a direction of 90 degrees with respect to the rubber sheet surface, leaving the cords at both ends.
The force required for peeling at a speed of 0 mm / min is indicated by N / 5 lines.

(3) Cord pull-out adhesive strength Shows the shear adhesive strength between the treated cord and rubber. The cord is embedded in an unvulcanized rubber block containing a carcass containing natural rubber as a main component, and at a temperature of 150 ° C. for 30 minutes, a pressing pressure of 50 kg / cm ² (initial value), or
Vulcanized at a temperature of 180 ° C. for 60 minutes at a pressing pressure (heat resistance value) of 50 Kg / cm ² , and then withdrawn the rubber block from the rubber block at a speed of 200 mm / min. It is displayed.

(4) Hardness Measured according to the method of JIS L1085.

Example 1 Polyepoxide compound, blocked polyisocyanate, rubber latex, di-2-ethylhexyl phthalate (hereinafter referred to as DOP)
35 parts PVC latex (film formation temperature: 160
C, Nippon Zeon Co., Ltd., G-151) was mixed at a solid content of 6.0% by weight, 20% by weight, 44% by weight, and 30% by weight, respectively, and the total solid content was 5.5% by weight. A liquid was obtained (treatment agent (1)).

An initial condensate having a resorcinol / formalin (R / F) molar ratio of 1 / 0.6 and a solid content of 65% by weight is dissolved under alkaline conditions to obtain a 9% by weight aqueous solution. 109 parts by weight of this is added to 180 parts by weight of a vinylpyridine / styrene / butadiene turbomer latex: 40% aqueous emulsion: Formalin:
5 parts by weight, 23 parts by weight of 33% by weight of an acetoxime-blocked phenylmetasidiisocyanate dispersion were added,
A liquid mixture having a solid content of 18% by weight aged for 48 hours was obtained (treatment agent (2)).

A multifilament yarn of 1500 denier / 384 filaments made of polyethylene terephthalate having an intrinsic viscosity of 0.95 was used, and the multifilament yarn was twisted at 40 T / 10 cm, and two of them were combined to 40 T / cm. To give a cord of 3000 denier / 768 filaments.

The cord was immersed in the treating agent (1) using a contributer treating machine (manufactured by CA Ritzler Co., Ltd., tire cord treating machine), dried at a temperature of 130 ° C. for 2 minutes, and subsequently dried. Heat treatment at a temperature of 240 ° C. for 1 minute, followed by immersion in the treating agent (2), followed by drying at a temperature of 170 ° C. for 2 minutes, followed by 240 ° C.
Heat treatment was performed at a temperature of 1 ° C. for 1 minute. In the obtained tire cord, the treating agent (1) was used as a solid component of the treating agent (1).
0% by weight and 1.7% by weight of the treating agent (2) were attached.
The obtained treatment cord is embedded in an unvulcanized rubber containing a carcass containing natural rubber as a main component, and is cured at a temperature of 150 ° C. for 30 minutes.
And then vulcanized at a temperature of 180 ° C. for 60 minutes and evaluated by the above method. Table 1 shows the results.

[Comparative Examples 1 to 3] The same treatment agent (1) as in Example 1 was used except that no PVC latex was added to the components of the treatment agent (1) used in Example 1. The treatment was carried out in the same manner as in Example 1 except that the adhesive amount (SPU) was changed as shown in Table 1 by changing the concentration of the treating agent (1). The obtained processing code was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 2 The treating agent (1) used in Example 1 was used as the treating agent (1), and the following was used as the treating agent (2). That is, an initial condensate having a resorcin / formalin (R / F) molar ratio of 1 / 0.6 and a solid content of 65% by weight is dissolved under alkaline conditions to obtain a 9% by weight aqueous solution. This is added in an amount of 109 parts by weight based on 180 parts by weight of a vinylpyridine / styrene / butadiene turbomer latex: 40% aqueous emulsion.
To this solution was added formalin: 5 parts by weight, 40% by weight of a cresol novolak type aromatic polyepoxide compound dispersion.
3 parts by weight, 33 parts by weight of acetoxime-blocked diphenylmethane diisocyanate dispersion (23 parts by weight) are added, and the mixture is aged for 48 hours. A solid content concentration: 18% by weight (treatment agent (2)) is used.

The same polyester filament cord as used in Example 1 was used, and was treated in the same manner as in Example 1 using the contributer treating machine used in Example 1. The obtained tire cord had 1.0% by weight of the treating agent (1) and 3.2% by weight of the treating agent (2) adhered thereto as solids of the treating agent. The obtained processing code was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Examples 3 to 5] In Example 1, as the treatment agent (1), the amount of PVC latex added and the treatment agent adhesion amount (SPU) were changed as shown in Table 1 and used. Other than that, it processed like Example 1. The obtained processing code was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6 P contained in the treating agent (1)
A treatment was performed in the same manner as in Example 1 except that a VC latex having a film formation temperature of 130 ° C. (manufactured by Zeon Corporation, G-576) was used, and the addition amount and the treatment agent adhesion amount were as shown in Table 1. did. The obtained processing code was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 4] PV contained in treating agent (1)
As the C latex, a film formation temperature: more than 200 ° C. (ZEST P-21 manufactured by Shin-Daiichi PVC Co., Ltd.) is used.
The treatment was performed in the same manner as in Example 1 except that the addition amount and the treatment agent adhesion amount were as shown in Table 1. The obtained processing code was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Examples 5 to 6] As the treating agent (1), P
The amount of the VC latex added and the amount of the treatment agent attached (S
PU) was used as varied as shown in Table 1.
The treatment was performed in the same manner as in Example 1. The obtained processing code was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 7 The following are used as the treating agent (3). That is, an initial condensate having a resorcin / formalin (R / F) molar ratio of 1 / 0.6 and a solid content of 65% by weight is dissolved under alkaline conditions to obtain a 9% by weight aqueous solution. This was mixed with a vinylpyridine / styrene / butadiene turbomer latex: 40% aqueous emulsion: 54 parts by weight and a DOP of 35 parts to give a solid concentration of 50 parts.
Wt% PVC latex (film formation temperature: 160
C, Nippon Zeon Co., Ltd., G-151): 54 parts by weight based on 36 parts by weight. To this solution, 2 parts by weight of formalin, 21 parts by weight of a 40% by weight cresol novolak type aromatic polyepoxide compound dispersion and 11 parts by weight of a 33% by weight acetoxime blocked diphenylmethane diisocyanate dispersion were added, followed by aging for 48 hours. Solid content concentration: A blended liquid (treatment agent (3)) of 18% by weight is used.

The same polyester filament cord as that used in Example 1 was used, and the same polyester filament cord was used as the treating agent (3) using the contributer processing machine used in Example 1.
After immersion, the substrate was dried at a temperature of 130 ° C. for 2 minutes, and subsequently subjected to a heat treatment at 240 ° C. for 1 minute twice. 7.1 wt% of the treating agent (3) was adhered to the obtained tire cord as a solid content of the treating agent. The obtained processing code was evaluated in the same manner as in Example 1. Table 1 shows the results.
Are shown together.

[Comparative Example 7] The same treatment as in Example 1 was used except that no PVC latex was added to the components of the treatment agent (1) used in Example 1 as the treatment agent (1). The treatment (1 bath method) was carried out in the same manner as in Example 7 except that the amount of the agent (1) attached (SPU) was as shown in Table 1. 8.2 wt% of the treating agent (1) was adhered to the obtained tire cord as a solid content of the treating agent. The obtained processing code was evaluated in the same manner as in Example 1. Table 1 shows the results.
Are shown together.

[0070]

[Table 1]

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C08L 67:00 D06M 101: 32 F term (reference) 4F072 AA04 AB05 AB24 AC10 AC12 AE15 AG06 AG13 AH03 AH22 AL18 4L033 AA07 AB01 AC11 BA08 BA69 CA15 CA34 CA50 CA68 CA70

Claims (5)

[Claims] 1. A polyester fiber having a film formation temperature of 2
A treating agent containing a vinyl halide group-containing compound, a polyepoxide compound and / or a blocked polyisocyanate compound and a rubber latex at a temperature of 00 ° C. or lower, wherein the content of the vinyl halide group-containing compound is reduced After being treated with the treating agent (1) in the range of 3 to 85% by weight based on the solid content of the agent, it is further treated with a treating agent (2) containing a blocked polyisocyanate compound and resorcinol-formalin rubber latex. A method for treating a polyester fiber for rubber reinforcement, which comprises treating the polyester fiber. 2. The method for treating a polyester fiber for rubber reinforcement according to claim 1, wherein a treatment agent (2) to which an aromatic epoxide compound is added is used. 3. A polyester fiber having a film formation temperature of 2
A treating agent containing a vinyl halide group-containing compound having a temperature of 00 ° C. or lower, an aromatic polyepoxide compound, and / or a blocked polyisocyanate compound, and a resorcinol-formalin rubber latex, which contains the vinyl halide group. A method for treating a rubber reinforcing polyester fiber, comprising treating with a treating agent (3) having a compound content of 3 to 85% by weight based on the solid content of the treating agent. 4. After the treatment with the treating agent (3),
The method for treating a polyester fiber for rubber reinforcement according to claim 3, wherein the treatment is carried out once or a plurality of times with a treating agent (4) containing resorcinol / formalin / rubber latex. 5. A treating agent (1) or a treating agent (3)
The method for treating a polyester fiber for rubber reinforcement according to claim 1, wherein the compound containing a vinyl halide group contained in the above is polyvinyl chloride.