JP3231535B2 - Adhesion treatment method between polyester fiber and ethylene propylene rubber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester fiber for a rubber composite. More specifically, the present invention relates to a technique for improving the adhesion between an ethylene propylene rubber and a polyester fiber. Examples of the product to which the polyester fiber of the present invention is applied include products such as a rubber hose, a diaphragm, a V-belt, and a conveyor belt having a fiber reinforcing layer or a reinforcing fiber base fabric.

[0002]

2. Description of the Related Art Polyester fibers have high strength and high Young's modulus, and are extremely useful as rubber reinforcing fibers for tires, hoses, belts, and the like. on the other hand,
In the field of hoses, rubber materials have been changing to have excellent high-temperature characteristics from the viewpoint of rubber materials, such as an increase in the temperature of an engine room of an automobile. One of them is ethylene propylene rubber, but it is very difficult to bond reinforcing fibers with the conventional method because the rubber has few double bonds in chemical structure and poor reactivity. It is. That is, when the polyester fiber is applied to the ethylene propylene-based rubber, the polyester fiber is relatively inert and has insufficient adhesion to the rubber matrix. Therefore, a chemical treatment method using various chemicals, for example, a method of treating a polyester fiber cord with a highly reactive chemical such as an epoxy compound or an isocyanate compound has been proposed. For example, it is characterized in that "a polyester fiber material after drawing is treated with a first treating agent containing a polyepoxide compound, and then treated with a second treating agent containing an ethylene urea compound represented by a general formula and resorcin-formalin rubber latex. (Japanese Patent Application Laid-Open No. 54-77794), "A linear aromatic polyester fiber is treated with a polyepoxide compound (A), a blocked polyisocyanate compound (B) and a rubber latex ( C), and then resorcinol-formalin rubber latex (RFL) is treated with an ethylene urea compound (D) represented by a general formula and an epoxy-modified phenol condensate (E) represented by a general formula. Characterized by being treated with a second treating agent to which is added at a constant weight ratio Processing method of Wei. "(JP 60-99076 JP), the" polyester-based synthetic fiber materials, after by adhering an epoxy compound having at least two epoxy groups, 150
Heat-treated at 260 ° C., and in the subsequent step, a rubber latex containing an ethylene urea compound represented by the general formula, a polybutadiene latex, and a terpolymer copolymer latex obtained by copolymerizing each component of styrene, butadiene and vinylpyridine are used. Treated with an adhesive solution containing the obtained resorcinol / formaldehyde latex.
A method for improving the adhesiveness of a polyester synthetic fiber material for reinforcing an ethylene / propylene copolymer rubber composition, wherein the heat treatment is performed at 60 ° C. (Japanese Patent Laid-Open No. Sho 60-21924)
No. 3) is disclosed. However, at present, even with these techniques, the adhesiveness of the polyester fiber to the ethylene / propylene copolymer rubber composition has not yet reached a sufficient level.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a high-pressure hose made of an ethylene propylene rubber matrix, in particular, as a reinforcing fiber for bonding to the rubber matrix. An object of the present invention is to provide a bonding treatment method for obtaining a polyester fiber having improved properties.

[0004]

According to the present invention, there is provided a method for treating a polyester twisted cord with a first treating agent comprising a polyepoxide compound and a terpolymer rubber latex of vinylpyridine / butadiene / styrene. A compound obtained by co-condensing parachlorophenol and resorcinol with formaldehyde in resorcinol-formalin rubber latex (RFL), while treating the polyester twist cord with a nip roller while nipping the same. Trinuclear (I) and pentanuclear (I
I), 7 polyester fiber karyoplast (III) blended special chlorophenol compounds shall be the main component, and blocked polyisocyanate compound as a crosslinking agent, characterized in that the treatment with the second treatment agent added Bonding method between ethylene and ethylene propylene rubber. ".

[0005]

Embedded image

The polyepoxide compound used in the first treating agent of the present invention is a compound containing at least two or more epoxy groups per molecule in an amount of 0.2 g equivalent or more per 100 g of the compound. Reaction products of polyhydric alcohols such as ethylene glycol, glycerol, sorbitol, pentaerythritol, and polyethylene glycol with halogen-containing epoxides such as epichlorohydrin,
Reaction products of polyhydric phenols such as resorcinol-bis (4-hydroxyphenyl) dimethylmethane, phenol-formaldehyde resin, resorcinol-formaldehyde resin and the above-mentioned halogen-containing epoxides, unsaturated compounds with peracetic acid or hydrogen peroxide, etc. And a polyepoxide compound obtained by oxidation of
-Epoxycyclohexene epoxide, 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6
Methyl-cyclohexylmethyl) adipate. Among them, a reaction product of a polyhydric alcohol and epichlorohydrin, that is, a polyglycidyl ether compound of a polyhydric alcohol is particularly preferred because it exhibits excellent performance. Such a polyepoxide compound is usually used as an emulsion. To make an emulsion or solution, for example, such a polyepoxide compound as it is,
Alternatively, if necessary, a solution dissolved in a small amount of a solvent is emulsified or dissolved using a known emulsifier, for example, sodium alkylbenzenesulfonate, sodium salt of dioctylsulfosuccinate, or a nonylphenolethylene oxide adduct.

The first treating agent comprises a rubber latex obtained by terpolymerizing the above-mentioned polyepoxide compound and vinylpyridine / butadiene / styrene, and the composition thereof is not particularly limited, but the epoxy concentration in the treating agent is 3% or less. Is preferable from the viewpoint of handleability. The solid content concentration of the first treating agent is 1 to 30% by weight, preferably 3 to 1% by weight based on the weight of the fiber.
Use at 5%.

[0008] The blocked polyisocyanate compound used in the second treating agent of the present invention is an adduct of a polyisocyanate compound and a blocking agent, and the block component is released by heating to produce an active polyisocyanate compound. It is. Examples of the polyisocyanate compound include polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, and triphenylmethane triisocyanate, or a mixture of these polyisocyanates and two active hydrogen atoms. A polyalkylene glycol containing a terminal isocyanate group obtained by reacting a compound having the above, for example, trimethylolpropane, pentaerythritol or the like with a molar ratio of the isocyanate group (-NCO) to the hydroxyl group (-OH) exceeding 1 Adduct polyisocyanate and the like can be mentioned. In particular, aromatic polyisocyanates such as triresin isocyanate, 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 resorcinol; aromatic secondary amines such as diphenylamine and xylidine; lactams such as phthalic imides, caprolactam and valerolactam; Oximes such as acetoxime, methyl ethyl ketone oxime and cyclohexane oxime, and sodium acid sulfite.

[0010] As a feature of the processing method, the nip Shinano polyester twisted code <br/> nip rollers during immersion treatment
Process . The nip roller may be outside or within the immersion bath. This is because the treating agent is sufficiently impregnated into the polyester twisted cord.

RFL applied as the second treating agent of the present invention
Is a mixture of an initial condensate, a special chlorophenol compound, and a rubber latex obtained by reacting resorcin formalin (RF) under an alkali or acidic catalyst. Regarding the compounding ratio of resorcin, formalin, and rubber latex, effects can be obtained by applying any of the known techniques. The compounding ratio of these special chlorophenol compounds and resorcinol, formalin, and rubber latex slightly changes depending on the compounding of the rubber to be adhered. In general,
The mixing ratio of the RF and the special chlorophenol compound is preferably 50/50 to 80/20 (weight ratio).

The special chlorophenol compound used herein is a compound obtained by co-condensing parachlorophenol and resorcinol with formaldehyde, and is a trinuclear (I) or pentanuclear compound represented by the following structural formula (Formula 3). (II), 7
Is to shall and the main component karyoplast (III).

[0013]

Embedded image

The rubber latex used in the second treating agent is obtained by blending the rubber latex terpolymerized with vinylpyridine / butadiene / styrene used in the first treating agent and polybutadiene latex. It is necessary to change the compounding ratio of these rubber latexes according to the characteristics of the rubber to be adhered, but terpolymer latex / polybutadiene latex is generally used in an amount of 70/30 to 30/70 (weight ratio). It is. However, the composition is not particularly limited.

[0015]

The polyester obtained by the present invention
The twisted cord has a surface treated with a treating agent containing an epoxy group, and a rubber latex made of a vinylpyridine / styrene / butadiene terpolymer having a high affinity for an ethylene propylene rubber as an adhered rubber. It is also treated with an adhesive made of a special halogen-containing chlorophenol compound having a high affinity for highly polar ethylene propylene rubber. Therefore, the vinyl pyridine / styrene / butadiene terpolymer rubber latex having a high affinity for the adhered rubber covers the cord surface, and the added crosslinking agent enhances the cohesive force of the treatment agent layer, which improves heat resistance and This leads to improved adhesion. In particular, many double bonds contained in the vinyl pyridine / styrene / butadiene terpolymer rubber latex play a large role. First, in the first treatment agent, the bond between the polyester fibers and the treatment agent layer is made strongly, this time, immersion treatment nip
Nip the polyester twisted cord with a roller
The first treatment agent penetrates into the fiber bundle
The air diffusion effect is exhibited, and the air diffusion property can be reduced. As a result, after the hose is formed, it is possible to prevent various liquids as a pressurizing medium from permeating into the reinforcing fiber layer from the hose end surface in the hose fitting portion under the pressurizing condition when the hose is used. This is a treatment method suitable for hose reinforcement, because it can greatly improve the service life and quickly transmit pressure and the like.

Hereinafter, the present invention will be described in detail with reference to examples. In addition, the evaluation method in an Example is as follows. <AD property> AD property (air diffusion property) corresponds to the air permeability of the hose blade layer. After placing the cords in a bundle of four in rubber and vulcanizing, air is applied at a pressure of ² kg / cm ² from one of the cord bundles (3000 denier × 4) exposed on the end face of the vulcanization block. For 5 minutes, and the amount of air permeated at that time was calculated from the change in water column pressure. The purpose is to evaluate the degree to which air passes through the voids in the cord. <Peeling Adhesive Strength> This is the strength when the hose is cut to a length of 1 inch and the rubber on the outside is peeled along the circumference of the hose. <Rubber Adhesion Rate> In the measurement of the peel adhesion, the residual adhesion rate of rubber on the blade cord after the outer rubber was peeled was determined.

[0017]

Examples 1-3, Comparative Examples 1-10 Polyethylene terephthalate fiber (manufactured by Teijin Limited, [η] = 0.90) 1
Twisted yarn core consisting of 500 denier / 250 filament
The steel was immersed in a yarn processing apparatus using the following first processing agent.

As a first treating agent, a polyepoxide compound (Denacol EX314: polyglycidyl ether, manufactured by Nagase Kasei Co., Ltd.) and a vinyl pyridine / styrene / butadiene terpolymer latex (Nippol 2518G)
L: manufactured by Zeon Corporation) in an active ingredient amount ratio of 1:
The mixture prepared in No. 1 and prepared with a 5% aqueous dispersion was used.

The twisted cord is immersed in the treatment liquid, and a nip roller made of rubber / rubber or rubber / steel is passed twice in the liquid to uniformly adhere to the inside, and dried at 100 to 150 ° C. for 1 to 3 minutes. Then at 130-200 ° C
Heat treatment was performed for 3 minutes.

Then, as a second treating agent (RFL), 17 parts of resorcinol and 14.9 parts of a 37% aqueous solution of formalin were reacted in 223.5 parts of water to which 13.3 parts of caustic soda was added to produce an RF resin. I got Next, a vinylpyridine / styrene / butadiene terpolymer latex (Nipol 2518GL: manufactured by Nippon Zeon Co., Ltd., solid content: 40%) and a polybutadiene rubber latex (Nipol LX111NF: Nihon Zeon Co., Ltd., solid content: 55%) ) In a solid content ratio of 1: 4 to 1: 2 (56.3 parts: 164 parts to 66.2 parts: 96.3).
And aged at room temperature for 24 hours. At this time, at the same time, 45 parts of an aqueous dispersion of a blocked polyisocyanate compound (Elastron BN-69: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content 40%) was added as a crosslinking agent. Immediately before use, to RF resin, four times the special chlorophenol compounds in solid content ratio (Denabon de, Nagase Kasei Co., Ltd.,
(Solid content: 20%) and used with sufficient stirring. The control of the viscosity and the amount of adhesion of the treating agent was adjusted by adding and diluting water to the treating agent.

The immersion treatment is performed in the second treatment agent,
After drying at 0 to 160 ° C for 1 to 3 minutes, heat treatment was performed at 180 to 235 ° C for 1 to 2 minutes. The obtained adhesive-treated polyester cord was braided at a crossing angle of 108 degrees, and was molded into a hose using ethylene-propylene-based unvulcanized rubber.
Steam vulcanization was performed at 0 ° C. for 40 minutes.

The rubber composition used for the evaluation is as follows.

EPDM 100 parts HAF-carbon black 120 parts Process oil (porafin) 90 parts Zinc white 5 parts Stearic acid 3 parts Vulcanizing agent 3.5 parts Vulcanization accelerator 2.5 parts

The results are shown in Tables 1 and 2. In Tables 1 and 2, the comparative examples are the cases where the mixing ratio of the rubber latex is changed, the case where no special chlorophenol compound is added or compounded, or the case where no crosslinking agent is compounded. According to the present invention, the adhesive peel strength and the rubber adhesion rate are good in a well-balanced manner. A is a vinylpyridine / styrene / butadiene terpolymer copolymer latex. B is polybutadiene latex. C is a blocked polyisocyanate compound. D is a special chlorophenol compound.

[0025]

[Table 1]

[0026]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08J 5/12 CFD C08J 5/12 CFD D06M 15/41 D06M 15/41 15/693 15/693 // B29K 21:00 B29K 21 JP-A-3-167372 (JP, A) JP-A-60-17177 (JP, A) JP-A-5-93368 (JP, A) JP-A-58-19375 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) D06M 13/00-15/72

Claims (1)

(57) [Claims] When a polyester twisted cord is treated with a first treating agent comprising a polyepoxide compound and a terpolymer rubber latex of vinylpyridine / butadiene / styrene, the polyester twisted cord is nipped by a nip roller. A trinuclear compound (I), which is a compound obtained by co-condensing parachlorophenol and resorcinol with formaldehyde on resorcinol-formalin rubber latex (RFL), 5 karyoplast (II), and the main component 7 karyoplast (III)
Adhesive treatment of polyester fiber and ethylene-propylene rubber, characterized in that to that blended special chlorophenol compounds, and blocked polyisocyanate compound as a crosslinking agent is processed in the second processing agent added. Embedded image