JPH0593370A - Improvement in adhesion of polyester fiber - Google Patents

Abstract

PURPOSE:To improve the adhesivity of polyester fibers to acrylic rubber materials by treating the polyester fibers with a treating agent comprising a RFL(resorcine formaldehyde latex) containing a specific chlorophenol compound and a specific rubber latex and subsequently treating the treated fibers with a treating agent comprising a RFL containing a specific rubber latex. CONSTITUTION:A polyester fiber cord is treated with the first treating agent comprising a RFL containing a rubber latex comprising a carboxyl group- containing vinyl pyridine-styrene-butadiene terpolymer and a chlorophenol compound having a mol.wt. distribution containing as main components a three- nuclear compound, a five-nuclear compound and a seven-nuclear compound of formula I, II and III produced by copoymerizing P-chlorophenol and resorcinol with formaldehyde. The treated polyester fiber cord is treated with the second treating agent comprising a RFL containing a mixture of an acrylic rubber latex as a rubber latex and the early condensate of RF, thus improving the adheiveness of the polyester fiber cord to rubber latexes, especially to acrylic rubber having high temperature characteristics.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a method for producing a polyester fiber for reinforcing acrylic rubber, which is resistant to high temperature vulcanization and secondary vulcanization and has good durability.

[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. on the other hand,
In the field of hoses, the temperature of the engine room of automobiles is becoming higher, and in view of the rubber material, it is changing to have excellent high-temperature characteristics. One of them is acrylic rubber. The rubber has poor reactivity and it is extremely difficult to bond the reinforcing fiber by the conventional method. That is,
When polyester fibers are used for these purposes, the surface is relatively inactive, so that the adhesiveness with a matrix such as rubber or resin is insufficient.

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.
The idea of using a chlorophenol compound, which is a good solvent for polyester, as an adhesive component has been around for a long time.
It has been used in the market as a product). However, this conventional chlorophenol compound is a compound in which parachlorophenol and resorcin are co-condensed with formaldehyde, and although they are expressed in the same way in terms of the structural formula, the molecular weight distribution shown in FIG. As can be seen, it contains a large amount of unreacted resorcin and parachlorophenol, and there are problems in the working environment, and the performance is not always sufficient.

[0004]

SUMMARY 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 an improved adhesiveness with an acrylic rubber matrix.

[0005]

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 consisting of 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),
A rubber latex of the first treating agent, which is mainly composed of pentanuclear (II) and 7-nuclear (III) and has a specific molecular weight distribution, is a carboxyl group-introduced vinylpyridine-butadiene-styrene ternary This is a method for improving adhesion of polyester fibers which are copolymers and whose rubber latex as the second treating agent is acrylic rubber latex.

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

[0007]

[Chemical 2]

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

The acryl-containing rubber latex referred to in the present invention is emulsified acrylic and added as an emulsion.

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.

[0011]

EFFECT OF THE INVENTION The polyester fiber obtained by the present invention is subjected to a dipping treatment with a first treatment agent consisting of resorcinol / formalin / carboxyl modified rubber latex to which chlorophenol, which is a good solvent for the fiber, is added, and then continuously applied. Resorcin formalin with acrylic rubber latex added, which has a high affinity with acrylic rubber.
Since it is treated with an adhesive composed of rubber latex, first, in the first adhesive, the bond between the polyester fiber and the adhesive layer is strengthened, and the carboxyl groups introduced on the surface of the used latex particles are It inactivates amines by reacting with and immobilizing amines generated from the. At the same time, the latex polymer forms a network structure due to the hydrogen bond between the carboxyl group and the pyridyl group and suppresses the permeation of the adhesion-inhibiting substance. Next, in the second adhesive, the acrylic rubber latex having a high affinity with the adhered rubber covers the fiber surface to enhance the adhesiveness. In particular, acrylic rubber is excellent in high-temperature properties, and thus is often used in a site exposed to a high temperature. Further, in order to develop rubber physical properties, it is often subjected to high-temperature secondary vulcanization. By applying the adhesion improvement method, the adhesion to the fiber and the adhesion-inhibiting component from the rubber side or the component degrading the adhesive layer from the rubber side are prevented, resulting in very low adhesive performance deterioration at high temperatures and good durability. Is what you get. 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 and dissolving the obtained solid in tetrahydrofuran, followed by 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) Particle size distribution of rubber latex Regarding the particle size distribution 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 within 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.

[0016]

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 put together, and the undertwist was applied 10 times / 10 cm to obtain a 3,000-de twisted cord.

As the 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, 340 g of rubber latex (40% water emulsion of acrylic rubber latex, Nipol 854E, manufactured by Nippon Zeon Co., Ltd.) was added to 2 parts of water.
00g, and after thoroughly stirring, add the resorcinol-formalin initial condensate solution while slowly stirring,
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 treated polyester cord was dried at 130 ° C. for 90 seconds using a dipping machine and then heat treated 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 containing acrylic rubber as the main component 15
Vulcanization was performed at 0 ° C. 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.

[0023]

[Table 1]

In the comparative example, a chlorophenol compound (Tamanol, manufactured by Arakawa Chemical Co., Ltd.), which is already on the market as a conventional chlorophenol compound, is used, and an acrylic rubber latex generally used as a conventional rubber latex product. Is used. According to the present invention,
Good balance between adhesion peel strength and rubber adhesion rate.

[Brief description of drawings]

[Figure 1] Conventional molecular weight distribution of phenol compounds

FIG. 2 Molecular weight distribution of special phenol compound according to the present invention

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.
Second made of formalin rubber latex (RFL)
In the adhesion improving method of treating with a treating agent, the special chlorophenol compound 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-nuclear compound (III) as a main component, having a specific molecular weight distribution, and the rubber latex of the first treating agent is a terpolymer of vinylpyridine-butadiene-styrene in which a carboxyl group is introduced. The method for improving adhesion of polyester fibers, wherein the rubber latex of the second treatment agent is acrylic rubber latex. [Chemical 1]