KR100995389B1 - Surface treating method of rubber-reinforcement polyester fiber, the first dipping formulation composition for the treating method, and rubber-reinforcement polyester fiber prepared therefrom - Google Patents

Abstract

The present invention relates to a surface treatment method of a polyester fiber for rubber reinforcement, a first treatment liquid composition used therein, and a polyester fiber for rubber reinforcement prepared therefrom, the surface of the polyester fiber for rubber reinforcement of the present invention The polyester fiber treated by the treatment method has excellent adhesion to rubber and has low rigidity, which can reduce tire failure rate when used as a tire cord, and improves workability and productivity because no toxic substances or impurities are generated in the treatment process. There is an effect of improvement.

Rubber Reinforcement, Polyester, Fiber, Epoxy, Diisocyanate, RFL

Description

SURFACE TREATING METHOD OF RUBBER-REINFORCEMENT POLYESTER FIBER, THE FIRST DIPPING FORMULATION COMPOSITION FOR THE TREATING METHOD, AND RUBBER-REINFORCEMENT POLYESTER FIBER PREPARED THEREFROM}

[Industrial use]

The present invention provides a surface treatment method of a polyester fiber for rubber reinforcement for imparting adhesion between rubber and polyester fiber, a primary treatment liquid composition used therein, and a polyester fiber for rubber reinforcement prepared by treatment with the treatment liquid. It is about.

[Private Technology]

 Polyester fiber represented by polyethylene terephthalate fiber used as a reinforcing material in the production of polyester tires has poor adhesiveness with rubber, and therefore, adhesives based on parachlorophenol-based RF resin (PEXUL), epoxy, and diisocyanate compounds are used. The method of improving the adhesion of synthetic fibers to rubber by coating the surface of synthetic fibers with a long time has been studied.                         

First, by using a parachlorophenol-based RF resin (PEXUL) first treatment of synthetic fibers with a primary treatment solution consisting of water, resorcinol, formalin, rubber latex and parachlorophenol-based RF resin (PEXUL) Thereafter, a method of treating with a secondary treatment liquid composed of RFL adhesives (compounds of lesosinol, formalin and rubber latex) generally prepared and used is known.

However, when the polyester fiber is treated with the primary treatment solution, it contains 70% or more of the ammonia water used as the main solvent of the parachlorophenol-based RF resin (PEXUL), and such ammonia is classified as a hazardous substance. This requires a separate purification facility to deal with this. In addition, in the field work can cause problems of workability and workplace contamination due to the unique smell.

In addition, due to the small gel, which is a type of impregnated dust generated by resorcinol, formalin, and parachlorophenol-based RF resin (PEXUL) after the impregnation treatment, the defective rate is finally increased during tire production, and the impregnated polyester fiber As the unit weight is also high, the cost burden of the producer increases.

In the case of an adhesive mainly composed of epoxy and diisocyanate compounds developed to solve this problem, the first treatment liquid composed of a mixed solution of diisocyanate and epoxy compound blocked with caprolactam or phenol is used. There is a method of treating an ester fiber and treating it with a secondary treatment liquid consisting of an RFL adhesive.

However, when the treatment solution is used, environmental pollution and gel generation may be remarkably improved, but the stiffness of the impregnated polyester fiber is considerably high after heat treatment due to the use of hardenable epoxy and diisocyanate. During the tire manufacturing process, a tip rise (also known as a 'curl up') phenomenon occurs and there is a problem in that the tire defective rate is increased.

In addition, in the above case, although a softener is used in the heat treatment process to lower the stiffness of the fiber, when used excessively, there is a problem that curling occurs in the treated polyester fiber itself. Therefore, it is necessary to lower the rigidity of the polyester fiber itself before treating the softener.

The present invention is to solve the above problems, an object of the present invention is excellent adhesion to rubber, low stiffness (stiffness) can reduce the tire failure rate, since no toxic substances or impurities in the treatment process The surface treatment method of the polyester fiber for rubber reinforcement which has the effect of improving workability and productivity improvement, the 1st process liquid used for the said processing method, and the polyester fiber for rubber reinforcement are provided.

The present invention to achieve the above object,
a) 100 parts by weight of demineralized water,
Sorbitol type epoxy 0.7 to 1.3 parts by weight,
1.5 to 2.5 parts by weight of blocked diisocyanate,
0.1 to 0.3 parts by weight of vinylpyridine latex (hereinafter referred to as 'VP latex'), a copolymer of vinylpyridine monomer, styrene and butadiene, and
0.1 to 0.5 parts by weight of an adhesive which is a compound of resorcinol, formalin and latex (hereinafter referred to as 'RFL adhesive')
Preparing a first treatment liquid composition comprising a;
b) passing through the first treatment liquid composition while applying tensile force to the polyester fibers;
c) drying the polyester fibers having passed through the first treatment liquid composition;
d) stretching the dried polyester fiber by heat treatment at a temperature of 220 to 250 ° C;
e) passing the heat treated polyester fiber through a RFL adhesive solution, which is a secondary treatment liquid; And
f) drying the polyester fiber passing through the RFL adhesive solution, the second treatment liquid, and stabilizing at a temperature of 220 to 240 ° C
It provides a surface treatment method of the polyester fiber for rubber reinforcement comprising a.

The present invention also relates to a rubber comprising 0.7 to 1.3 parts by weight of sorbitol type epoxy, 1.5 to 2.5 parts by weight of sealed diisocyanate, 0.1 to 0.3 parts by weight of VP latex, and 0.1 to 0.5 parts by weight of RFL adhesive. Provided is a primary treatment liquid for surface treatment of reinforcing polyester fibers.

The present invention also provides a polyester fiber for rubber reinforcement having an adhesive force of 14 kgf or more and a stiffness of 7.0 g / cord or less, treated by the above method.

Hereinafter, the present invention will be described in more detail.

The present invention uses a primary treatment liquid mainly composed of epoxy and diisocyanate and a secondary treatment liquid mainly composed of RFL adhesive to impart adhesiveness to the polyester fiber for rubber reinforcement.

In the present invention, the primary treatment solution provides the adhesion between PET and RFL, and the secondary treatment solution serves to bond the primary treated PET with rubber.

More detailed components and process conditions of the treatment solution are as follows.                     

First, to prepare the primary treatment liquid composition, 0.7 to 1.3 parts by weight of sorbitol type epoxy, 1.5 to 2.5 parts by weight of sealed diisocyanate, 0.1 to 0.3 parts by weight of VP latex, and RFL adhesive based on 100 parts by weight of pure water (Compound of resorcinol, formalin, latex) 0.1 to 0.5 parts by weight are mixed.

In the preparation of the primary treatment liquid composition, when 100 parts by weight of pure water is added, the stiffness of the polyester fiber increases when the sum of the epoxy and the blocked diisocyanate exceeds 3.0, and the content of the RFL adhesive is 1.0. If it exceeds the weight part, the adhesive force may drop.

The blocked diisocyanate used in the preparation of the primary treatment liquid composition may be one in which the terminal isocyanate group is blocked by caprolactam or phenol. In addition, the said VP latex is a copolymer of a VP (vinylpyridine) monomer, styrene, and butadiene, and is added in order to raise the viscosity of a process liquid composition. The RFL adhesive is made of a compound of resorcinol (R), formalin (F), and latex (L), and is added to lower the glass transition temperature (Tg) of the treatment liquid composition, and 12 to 84 hours after makeup is completed. The old one can be used.

After the preparation of the primary treatment liquid composition is finished, it is passed through the prepared primary treatment liquid composition while applying a tensile force to the polyester fiber. At this time, the passing speed is preferably 60 to 80 m / min, in order to prevent the treatment liquid composition from penetrating into the polyester fiber, the tensile force is maintained at 0.7 g / denier or more, preferably 0.7 to 1.5 g Keep it denier.                     

The polyester fiber passing through the first treatment liquid composition is dried in a drying zone, and the drying temperature is preferably 145 to 155 ° C. The dried polyester fiber is stretched by heat treatment at a temperature of 220 to 250 ° C. in a stretching zone. If the heat treatment temperature is less than 220 ℃ dimensional stability of the tire cord is reduced due to the lack of thermal history, if it exceeds 250 ℃ PET may be thermally decomposed strength may be lowered.

After the heat treatment (stretching) of the polyester fiber is passed through a secondary treatment solution mainly composed of RFL adhesive, the polyester fiber passed through the secondary treatment solution is subjected to a drying process again, the stabilization area By stabilizing by heat treatment at a temperature of 220 to 240 ℃ in the (normalizing zone), it is possible to give an adhesive force to the surface of the polyester fiber for rubber reinforcement.

However, the residence time in the stretch area and the stabilization area is preferably 40 to 50 seconds. If the residence time is less than 40 seconds, the sufficient stretching and stabilizing effect may not be achieved, and if it exceeds 50 seconds, the adhesive strength of the polyester fiber may be lowered.

The polyester fiber for rubber reinforcement treated through the above process has an adhesive force of 14 kgf or more, preferably 14 to 16 kgf. In addition, the rubber reinforcing polyester has a rigidity of less than 7.0 g / cord, preferably has a rigidity of 5.0 to 7.0 g / cord.

Accordingly, the polyester fiber for rubber reinforcement treated with the primary treatment liquid composition of the present invention is a gel that causes environmental problems, workability, and tire failure, which are problems in using the treatment liquid using a parachlorophenol-based RF resin. Suitable for use as a soft polyester tire cord without the problem of tip rise in tire manufacturing due to high stiffness, which is a problem of production and high cost, and a problem of using epoxy and diisocyanate. Do.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

Example 1

0.7 parts by weight of sorbitol type epoxy, 1.7 parts by weight of diisocyanate sealed with phenol, VP latex (40% by weight of copolymer copolymerized with VP monomer, styrene and butadiene in a ratio of 15:15:70) based on 100 parts by weight of pure water 0.1 weight part and 0.1 weight part of RFL adhesives were mixed, and the 1st process liquid composition was prepared. Polyester fibers (1500 denier / 2 sum) were impregnated into the prepared primary treatment solution composition, at which time the tension was maintained to be 1.37 g / denier, and the rate of passage of the primary treatment solution composition of the impregnated fiber Maintained between 60 and 80 m / min. The polyester fiber passed through the first treatment liquid composition was dried at 150 ° C. for 2 minutes in a drying zone, and then heat-treated at 245 ° C. in a stretching zone. The polyester fiber after the heat treatment process was again impregnated in RFL adhesive solution (secondary treatment solution), dried at a temperature of 150 ℃, stabilized at a temperature of 235 ℃ to prepare a polyester fiber for rubber reinforcement.                     

[Example 2]

In preparing the first treatment liquid composition, a polyester fiber for rubber reinforcement was prepared in the same manner as in Example 1 except that the content of the RFL adhesive was added in an amount of 0.5 parts by weight based on 100 parts by weight of pure water.

Comparative Example 1

A polyester fiber for rubber reinforcement was prepared in the same manner as in Example 1 except that the RFL adhesive was not added when preparing the first treatment liquid composition.

Comparative Example 2

In preparing the first treatment liquid composition, a polyester fiber for rubber reinforcement was prepared in the same manner as in Example 1 except that the content of the RFL adhesive was added in an amount of 8.0 parts by weight based on 100 parts by weight of pure water.

The glass transition temperature and the adhesive strength and stiffness of the polyester fiber for rubber reinforcement of the first treatment liquid composition prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured according to the following methods, specific treatment conditions and the Measurement results of glass transition temperature, adhesion strength, and stiffness are summarized in Table 1 below.

Glass Transition Temperature: DSC 1st Run

-Adhesive force: After the tire rubber is adhered to both ends of the polyester fiber for rubber reinforcement, it is measured under the vulcanization condition (160 ℃, 20 minutes, 20kgf / ㎠ (vulcanization pressure), 3 / 8in (sample diameter)) (H- TEST)

-Stiffness: ASTM D 885M                     

TABLE 1

Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 The first
Of the treatment liquid composition
Ingredient ratio pure 100 100 100 100 Epoxy 0.7 0.7 0.7 0.7 Diisocyanate 1.7 1.7 1.7 1.7 VP latex 0.1 0.1 0.1 0.1 RFL Adhesive 0.1 0.5 0.0 8.0 Tg (° C.) of the first treatment liquid composition 41.6 34.0 49.4 - 2nd
Treatment solution
Ingredient ratio RFL Adhesive 100 100 100 100 1st dipping tensile force (kgf / cord) 2.3 2.3 2.3 2.3 Temperature Drying zone 150 150 150 150 Kidney zone 245 245 245 245 stabilize 235 235 235 235 Rubber modification
Polyester fiber Adhesion
(kgf) 15.5 15.6 15.9 8.0 Stiffness
(g / cord) 6.3 6.0 9.0 6.0

As shown in Table 1, the polyester fiber for rubber reinforcement treated by Examples 1 and 2 of the present invention, which does not include RFL, exhibits an adhesive force of 15.5 kgf or more, and shows a stiffness of about 6.0 g / cord. It can be seen that there is an excellent adhesion and the effect of preventing curl-up (curl-up) occurs.

The polyester fiber treated by the surface treatment method of the polyester fiber for rubber reinforcement of the present invention has excellent adhesion to rubber and has low rigidity, thereby reducing tire failure rate when used as a tire cord, and Since impurities are not generated, there is an effect of improving workability and productivity.

Claims (6)

a) 100 parts by weight of demineralized water,    Sorbitol type epoxy 0.7 to 1.3 parts by weight,    1.5 to 2.5 parts by weight of blocked diisocyanate,    0.1 to 0.3 parts by weight of vinylpyridine latex (VP latex), a copolymer of vinylpyridine monomer, styrene and butadiene, and    0.1 to 0.5 parts by weight of an adhesive (RFL adhesive) which is a compound of resorcinol, formalin and latex    Preparing a first treatment liquid composition comprising a; b) passing through the first treatment liquid composition while applying tensile force to the polyester fibers; c) drying the polyester fibers having passed through the first treatment liquid composition; d) stretching the dried polyester fiber by heat treatment at a temperature of 220 to 250 ° C; e) passing the heat treated polyester fiber through a RFL adhesive solution, which is a secondary treatment liquid; And f) drying the polyester fiber passing through the RFL adhesive solution, the second treatment liquid, and stabilizing at a temperature of 220 to 240 ° C Surface treatment method of the polyester fiber for rubber reinforcement comprising a. delete 100 parts by weight of demineralized water; 0.7 to 1.3 parts by weight of sorbitol type epoxy; 1.5 to 2.5 parts by weight of blocked diisocyanate; 0.1 to 0.3 parts by weight of vinylpyridine latex (VP latex) which is a copolymer of vinylpyridine monomer, styrene and butadiene; And 0.1 to 0.5 parts by weight of an adhesive (RFL adhesive) which is a compound of resorcinol, formalin and latex Primary treatment liquid composition for surface treatment of the polyester fiber for rubber reinforcement comprising a. The first treatment liquid composition according to claim 3, wherein the first treatment liquid has a glass transition temperature of 33 to 45 ° C. A polyester fiber for rubber reinforcement having a surface treatment by the method of claim 1 having an adhesion of 14 kgf or more and a rigidity of 7.0 g / cord or less. The polyester fiber for rubber reinforcement according to claim 5, having an adhesion of 14 to 16 kgf and a rigidity of 5.0 to 7.0 g / cord.