JPH0593369A - Method for improving adhesion of polyester fibers - Google Patents

Abstract

(57) [Summary] [Object] An object of the present invention is to improve the adhesion of polyester fibers, particularly to rubber materials. [Structure] In an adhesion improving method in which polyester fiber is treated with a first treatment agent containing a special chlorophenol compound, resorcinol, formalin, and rubber latex, and subsequently treated with a second treatment agent containing resorcinol, formalin, and rubber latex. , A special chlorophenol compound,
It is a compound obtained by copolymerizing parachlorophenol and resorcin with formaldehyde, and has a specific molecular weight distribution mainly composed of a trinuclear, a pentanuclear, and a 7 nuclide represented by a specific structural formula. The rubber latex as the treating agent is a terpolymer of vinylpyridine / styrene / butadiene having a carboxyl group introduced, and the rubber latex as the second treating agent has a specific particle size distribution.
A method for improving the adhesion of polyester fibers that are styrene-butadiene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a process for producing a polyester fiber for rubber reinforcement which has a high durability and can be used at high temperatures.

[0002]

2. Description of the Related Art Polyester fiber has high strength and high Young's modulus, and it is extremely useful as a fiber for reinforcing rubber of tires, hoses, belts, etc.

When polyester fibers are used for these purposes, the surface thereof is relatively inactive and the adhesiveness to the matrix of rubber or resin is insufficient at present.

Therefore, a chemical treatment method using various chemical agents, for example, a method of treating with a highly reactive chemical agent such as an epoxy compound or an isocyanate compound has been proposed and put into practical use. In addition, the idea of using a chlorophenol compound, which is a good solvent for polyester, has been around for a long time, and it has been actually marketed and used as VALCABOND (ICI product) or Tamanol (Arakawa Chemical Co., Ltd. product). However, this conventional chlorophenol compound is one in which parachlorophenol and resorcin are co-condensed with formaldehyde, and is represented in the same structural formula as that of the present invention. As can be seen from the molecular weight distribution shown, it contains a large amount of unreacted resorcinol and parachlorophenol, which is not always sufficient for the recent demand for improvement in durability.

[0005]

OBJECTS OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a polyester fiber having improved adhesion to a rubber matrix.

[0006]

That is, according to the present invention, a polyester fiber is treated with a first treating agent containing a special chlorophenol compound, resorcin, formalin, and rubber latex, and subsequently, resorcin, formalin, rubber latex (R
In the adhesion improving method of treating with a second treating agent containing FL), the special chlorophenol compound is a compound in which parachlorophenol and resorcin are co-condensed with formaldehyde, and a trinuclear body represented by the following structural formula ( I),
The rubber latex of the second treatment agent, which has a 5-nuclear body (II) and a 7-nuclear body (III) as the main components and has a specific molecular weight distribution, is a terpolymer of vinylpyridine-butadiene-styrene into which a carboxyl group has been introduced. A method for improving adhesion of polyester fibers, which is a polymer and wherein the rubber latex as the second treating agent is composed of vinyl pyridine / styrene / butadiene having a specific particle size distribution.

The special chlorophenol compound referred to in the present invention is a compound obtained by co-condensing parachlorophenol and resorcin with formaldehyde, and is represented by the following structural formula: trinuclear body (I), pentanuclear body (II) ), 7 nucleolar (III)
It is a special chlorophenol compound consisting of, and has a specific molecular weight distribution as shown in FIG.

[0008]

[Chemical 2]

The carboxyl-modified rubber latex as referred to in the present invention is a vinyl pyridine-butadiene-styrene terpolymer latex which is generally used and has a carboxyl group introduced therein.

As used in the present invention, the rubber latex having two particle sizes, that is, a small particle and a large particle, refers to a particle size distribution of latex particles in the emulsion as shown in the graph (FIG. 3). Each has a distribution peak at 350 nm or more.

The RFL applied in the present invention is resorcin
It is a mixture of an initial condensate obtained by reacting formalin in the presence of an alkali or an acidic catalyst and a rubber latex, and regarding the compounding ratio of resorcin, formalin and rubber latex, any known technique is effective. Be done.

[0012]

EFFECT OF THE INVENTION The polyester fiber obtained by the present invention is immediately treated with a small particle after being dipped in a first treating agent consisting of resorcin / formalin / carboxyl modified rubber latex to which chlorophenol which is a good solvent for the fiber is added. Since the treatment is performed with an adhesive composed of resorcinol-formalin-rubber latex using a rubber latex composed of two large particles, first, in the first adhesive, the polyester fiber and the adhesive layer are bonded to each other. The carboxyl group which is made strong and introduced on the surface of the used latex particles reacts with amines generated in the rubber or the like to immobilize and deactivates the amine. At the same time, the latex polymer forms a network structure due to the hydrogen bond between the carboxyl group and the pyridyl group to suppress the permeation of amines. Next, in the second adhesive, the rubber latex having a small particle size covers the surface of the fiber, and the rubber latex having a large particle size covers the outside thereof, so that the adhesion to the fiber and the adhesion-inhibiting component or the adhesive layer-degrading component from the rubber side are obtained. By preventing the above, it is possible to obtain an adhesive performance with good durability, in which the deterioration of the adhesive performance under a high temperature is extremely small.

Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, various performances were measured by the following methods.

(1) Molecular weight distribution of chlorophenol compound The molecular weight distribution of the chlorophenol compound is measured by vacuum-drying the compound, dissolving the obtained solid in tetrahydrofuran, and subjecting it to gel permeation chromatography or liquid chromatography. It was measured by.
Although it depends on the characteristics of the column used, even if the dissolved concentration of the solid content is different, there is almost no difference in the obtained distribution shape.

(2) Distribution of particle size of rubber latex Regarding the distribution of particle size of rubber latex, the particle size and frequency are measured from a photograph taken by observing with a scanning electron microscope after vacuum drying the rubber latex. It is a graph.

(3) SPU (Solid Pick Up) The adhesion amount was determined from the weight difference before and after the adhesion treatment.

(4) Adhesion Performance (Peeling Adhesion between Plies) 30 cords are arranged in 1 inch, and both sides thereof are sandwiched by a rubber sheet having a thickness of 0.4 mm. Two of these are stacked and vulcanized under predetermined conditions. Then 5 between the two layers with cords
Peel at a speed of 0 mm / min and measure the adhesive strength at that time. In addition, the rubber adhesion state after peeling is observed and ranked to obtain the rubber adhesion amount.

[0018]

Examples 1 to 4, Comparative Examples 1 to 4 Polyethylene terephthalate fiber (manufactured by Teijin Ltd., [η] = 0.90) 150
Two multifilaments consisting of 0 de-250 fil were combined, respectively, and each twisted and twisted 40 times / 10 cm to obtain a cord of 3000 de.

As a first treatment liquid, a special chlorophenol compound having a constant molecular weight distribution obtained by co-condensing parachlorophenol and resorcin with formaldehyde (Denabond; an aqueous ammonia solution of a chlorophenol compound manufactured by Nagase Kasei Co., Ltd.) , Phenol trinuclear,
A 20% by weight aqueous ammonia dispersion containing 5 or 7 nuclide as a main component and 40% water emulsion of rubber latex (styrene-butadiene and vinyl-pyridine terpolymer partially carboxyl-modified), Nipo Guard
A mixture of Z-500, manufactured by Zeon Corporation and water in a weight ratio of 2: 1: 4 is prepared.

On the other hand, as a second treating agent, 30 g of 28% aqueous ammonia solution was added to 260 g of water and stirred well, and 60 g of a resorcin-formalin initial condensation product (40% acetone solution) condensed in advance with an acidic catalyst in this aqueous solution. Was added and sufficiently stirred to disperse. Next, a rubber latex (a terpolymer of styrene-butadiene and vinyl-pyridine, whose particle size distribution has peaks at 80 nm and 400 nm, a 40% water emulsion, Nippol TG-1008, manufactured by Nippon Zeon Co., Ltd. ) 340
After adding g to 200 g of water and stirring sufficiently, the resorcinol-formalin initial condensate solution was slowly added with stirring, and then 20 g of formalin solution (37%) was added to obtain an aqueous adhesive. The adhesive solution was aged at 20 ° C. for 48 hours.

After treating the above polyester cord with the above-mentioned first treating agent, the polyester cord is dried with a dipping machine at 130 ° C. for 90 seconds,
Heat treatment was performed at 240 ° C. for 60 seconds.

Then, a dipping treatment is performed in the second treatment agent,
Similar to the treatment with the first treatment agent, a dipping machine was used to dry at 130 ° C. for 90 seconds and then heat treatment was performed at 235 ° C. for 60 seconds.

The resulting adhesive-treated polyester cord is
Embedded in unvulcanized rubber whose main component is natural rubber, 150 ° C
Was vulcanized for 30 minutes, and the peel adhesion between plies and the rubber adhesion rate after peeling were measured.

The results are shown in Table 1.

[0025]

[Table 1]

In the comparative example, a chlorophenol compound (Tamanol, manufactured by Arakawa Chemical Co., Ltd.), which has already been put on the market as a conventional product of chlorophenol compound, is used, and vinyl pyridine which has been conventionally used as a conventional product of rubber latex is used. -Styrene / Butadiene / Rubber latex (for example, Pylatex FS, manufactured by Sumitomo Nogatak Co., Ltd.). According to the present invention, the adhesive peel strength and the rubber adhesion rate are well balanced and good.

[Brief description of drawings]

Figure 1: Molecular weight distribution map of conventional chlorophenol compounds

FIG. 2 is a molecular weight distribution map of the special chlorophenol compound according to the present invention.

Fig. 3 Particle size distribution chart of rubber latex particles

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display area D06M 15/41 // D06M 101: 32

Claims (1)

[Claims] 1. A polyester fiber is treated with a first treatment agent containing a special chlorophenol compound, resorcin, formalin, and rubber latex, and then resorcin.
In the adhesion improving method of treating with a second treatment agent containing formalin rubber latex (RFL), the special chlorophenol compound is a compound in which parachlorophenol and resorcin are co-condensed with formaldehyde and represented by the following structural formula. A vinyl latex having a carboxyl group introduced therein, which is composed mainly of a trinuclear (I), a pentanuclear (II), and a 7-nuclear (III) and has a specific molecular weight distribution and a rubber latex as a second treating agent. A method for improving adhesion of polyester fibers, which is a pyridine-butadiene-styrene terpolymer and wherein the rubber latex of the second treating agent is vinyl pyridine / styrene / butadiene having a specific particle size distribution. .. [Chemical 1]