JP3188588B2 - Processing method of polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite of fiber and rubber, and more particularly, to a bonding technique between chloroprene rubber and nitrile butadiene rubber and polyester fiber.
Products to which the present invention can be applied include rubber hoses having a fiber reinforcing layer and a fiber base fabric, diaphragms, V-belts, conveyor belts, etc., and are particularly suitable for rubber hoses used for fluid flow paths.

[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, recently, as the temperature of the engine room of an automobile increases, a material having excellent high-temperature characteristics is demanded from the viewpoint of rubber material. As one of them, nitrile butadiene rubber (NBR) is used for the inner layer of the hose, and chloroprene rubber (C
A two-layer hose using R) has been developed. Chloroprene rubber has few double bonds in its chemical structure and is poor in reactivity, and it is extremely difficult to bond polyester reinforcing fibers by the conventional method. Therefore, a chemical treatment method using various chemicals, for example, a method of treating with a highly reactive chemical such as an epoxy compound or an isocyanate compound has been proposed and put into practical use. For example, "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. A method of treating a polyester fiber material for rubber reinforcement characterized by the following: (Japanese Patent Application Laid-Open No. 54-77794). However, at present, even with these techniques, the adhesiveness of the polyester fiber to the chloroprene 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 an object of the present invention is to provide a hose having a chloroprene rubber matrix as an outer layer and a nitrile-butadiene rubber matrix as an inner layer. While expressing strong adhesion performance with the outer layer rubber,
It is an object of the present invention to provide a method for treating a polyester fiber having a practical level of adhesion performance with the inner layer rubber.

[0004]

According to the present invention, there is provided (claim 1) a polyester fiber cord to which a polyepoxide compound is preliminarily applied, to resorcinol-formalin rubber latex (RFL), and parachlorophenol and resorcinol to formaldehyde. A polyester fiber treated with a treating agent to which a blocked polyisocyanate compound is added as a cross-linking agent, wherein the compound obtained by co-condensing parachlorophenol and resorcinol with formaldehyde has a structural formula Trinuclear (I), pentanuclear ( II ), heptanuclear ( III ) represented by 1)
A click Rollo phenolic compound mainly containing, RFL
The rubber latex used is a solid content ratio of chloroprene rubber latex and nitrile butadiene rubber latex
Is a mixed latex having a ratio of 60/40 to 95/5 . ".

[0005] A polyepoxide compound previously applied to a polyester fiber is a compound containing at least two epoxy groups per molecule in an amount of 0.2 g equivalent or more per 100 g of the compound, and ethylene glycol, glycerol, sorbitol, pentaerythritol, Reaction products of polyhydric alcohols such as polyethylene glycol with halogen-containing epoxides such as epichlorohydrin, and polyhydric phenols such as resorcinol bis (4-hydroxyphenyl) dimethylmethane, phenol-formaldehyde resin and resorcinol-formaldehyde resin Examples of the reaction product with the halogen-containing epoxide, a polyepoxide compound obtained by oxidizing an unsaturated compound with peracetic acid or hydrogen peroxide, and the like.
Epoxycyclohexene epoxide, 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6-methyl-cyclohexylmethyl) adipate and the like can be mentioned. 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 or a solution. In order to prepare an emulsion or a solution, for example, such a polyepoxide compound as it is, or a solution obtained by dissolving it in a small amount of a solvent, if necessary, is a known emulsifier, for example, sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol ethylene oxide. Emulsify or dissolve using adducts and the like. It is preferable from the viewpoint of production that the polyepoxide compound is applied by oiling in the step of drawing the polyester fiber and subsequently heat-set.

[0006] A blocked polyisocyanate compound is an adduct of a polyisocyanate compound and a blocking agent, and the block component is released by heating to generate an active polyisocyanate compound. Examples of the polyisocyanate compound include polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, and triphenylmethane triisocyanate, or those polyisocyanates and two or more active hydrogen atoms. Compounds such as trimethylolpropane and pentaerythritol with an isocyanate group (-
A polyalkylene glycol adduct polyisocyanate having a terminal isocyanate group, which is obtained by reacting the NCO) with a hydroxyl group (—OH) at a molar ratio exceeding 1; 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.

[0008] RFL adhesive treatment agent is a mixture of precondensate and click Rollo phenol compound and a rubber latex obtained by the resorcinol-formalin are reacted under alkaline or acidic catalysts, of resorcinol formalin rubber latex Regarding the compounding ratio, an effect can be obtained by applying any of the known techniques. Depending on the composition of the rubber to be adhered,
This results Lac Rollo phenolic compound, mixing ratio of the resorcinol-formalin-rubber latex can vary slightly. In general, the mixing ratio of the aforementioned RF and click Rollo phenolic compound, 50 / 50-80 / 20 (weight ratio) is preferably used.

The chlorophenol compound of the present invention is a compound obtained by co-condensing parachlorophenol and resorcin with formaldehyde.
It has a nucleus (I), a pentanucleus ( II ), and a heptanucleus ( III ) as main components and has a molecular weight distribution profile shown in FIG. Incidentally, FIG. 1 is a molecular weight distribution of a conventional phenol compound.

The rubber latex used in the RFL adhesive agent has a solid content ratio of chloroprene rubber latex and nitrile butadiene rubber latex of 60 / 40-95.
/ 5 is obtained by mixing such that, you the ratio of chloroprene rubber latex higher than nitrile-butadiene rubber latex.

[0011]

The surface of the polyester fiber obtained according to the present invention contains a rubber component having a diene bond having a high affinity with the chloroprene rubber to be adhered, and at the same time has a high affinity with the chloroprene rubber. high, and it is coated with an adhesive coating containing a torque Rollo phenolic compound Yusuke <br/> a chloro group. In addition, the added crosslinking agent enhances the cohesive force of the adhesive layer, and contributes to improvement in heat resistance and development of adhesiveness. Since a certain amount of nitrile-butadiene rubber latex is mixed, it also has adhesiveness to nitrile-butadiene rubber.

Hereinafter, the present invention will be described specifically with reference to examples. In addition, the evaluation method in an Example is as follows. <Preparation of Rubber Hose> The obtained adhesive-treated polyester cord was first braided around a nitrile-butadiene-based unvulcanized rubber wound around an iron core at a crossing angle of 108 °, and a chloroprene-based unvulcanized rubber was wound thereon. Molded into 1
Steam vulcanization was carried out at 50 ° C. for 40 minutes to prepare a hose in which the inner rubber layer was a nitrile butadiene rubber and the outer rubber layer was a chloroprene rubber, and the peel adhesion and the rubber adhesion after peeling were measured. <Hose Peeling Adhesive Force> The peeling adhesive force with the outer layer rubber is represented by the strength when a hose is cut to a length of 1 inch and the outer rubber is peeled along the circumference of the hose. The peel adhesion to the inner rubber indicates the strength when the blade reinforcing fiber layer is peeled from the inner rubber along the circumference of the hose. <Rubber Adhesion Rate> In the peel adhesion measurement, the residual adhesion rate of rubber on the front or back surface of the blade cord after peeling was determined.

The composition of the rubber used in the evaluation is as follows. Neoprene W 100 parts Chloroprene rubber manufactured by Showa Denko Dupont Co. Antioxidant 2 parts Anti-crack agent 3 parts Magnesium oxide 4 parts MAF-carbon black 20 parts Hard clay 80 parts Process oil 12 parts Zinc oxide 5 parts Vulcanization accelerator 1 part

[0014]

Examples 1 to 3 and Comparative Examples 1 to 4 Polyethylene terephthalate fibers (manufactured by Teijin Limited, to which a polyepoxide compound was previously added in an amount of 0.4% by weight with respect to the fiber weight) in a polyester fiber spinning step (drawing step). η] 0.90) 1
A multifilament consisting of 500 denier-250 filaments was twisted eight times per 10 cm to form a cord, which was then immersed in the following RFL adhesive using a cord processing apparatus.

As an RFL, 12.5 parts of an initial condensate of resorcinol and formalin (Sumikanol 700S, manufactured by Sumitomo Chemical Co., Ltd., solid content concentration: 65%) were mixed with 3.1 parts of a sodium hydroxide aqueous solution (concentration: 10%), ammonia and 9 parts of water (concentration: 28%) and 10.6 parts of formalin (concentration: 37%) are added to 102.3 parts of water, and mixed and stirred. Next, chloroprene rubber latex (product name: LT-50, manufactured by Denki Kagaku Co., Ltd., solid content concentration: 50%) was added to the aqueous solution.
8 parts and 66.2 parts of nitrile butadiene rubber latex (trade name: Nippol LX1562, solid content concentration: 40%, manufactured by Zeon Corporation) are added and mixed, and aged at room temperature for 24 hours. At this time, at the same time, an aqueous dispersion of a blocked polyisocyanate compound (trade name: DM601) was used as a crosslinking agent.
1, 64.1 parts of Meisei Chemical Co., Ltd., solid content 40%). Immediately before use, to RF resin, 4 times the click Rollo phenol compound in solid content ratio (trade name: Denabondo E, Nagase Kasei Co., Ltd., solid content 20%) was added,
Use with good stirring. The viscosity and amount of the treatment agent are controlled by adding and diluting water to the treatment agent.
Immerse the treatment code in this RFL adhesive,
After drying at 160 ° C for 1 to 3 minutes,
Heat treatment was performed for 2 minutes. If the treatment is carried out at a temperature higher than this temperature, the stability of the chloroprene rubber latex decreases, and sufficient adhesion performance is not exhibited. Table 1 shows the results.

[0016]

[Table 1]

In the comparative example, the mixing ratio of the chloroprene rubber latex and the nitrile butadiene rubber latex is higher than that of the nitrile rubber latex, and the present invention is well-balanced in both adhesive peel strength and rubber adhesion rate.

[Brief description of the drawings]

FIG. 1. Conventional phenolic compound molecular weight distribution

FIG. 2 shows the molecular weight distribution of the chlorophenol compound according to the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-161573 (JP, A) JP-A-3-40875 (JP, A) JP-A-1-132883 (JP, A) JP-A-5-205 98575 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 13/00-15/72

Claims (1)

(57) [Claims] 1. A polyester fiber cord preliminarily provided with a polyepoxide compound is formed from resorcinol-formalin-
A method for treating polyester fibers, comprising mixing a compound obtained by co-condensing parachlorophenol and resorcinol with formaldehyde into a rubber latex (RFL), and treating with a treating agent to which a blocked polyisocyanate compound is added as a crosslinking agent. trinuclear compounds chlorophenol and resorcin it was co-condensing with formaldehyde is represented by the following structural formula (formula 1) (I), 5 karyoplast (I
I), 7 karyoplast (III) is a click Rollo phenol compound as a main component, rubber latex used in the RFL is the solid content of the chloroprene rubber latex and nitrile-butadiene rubber latex at 60 / 40-95 / 5 A method for treating polyester fiber, which is a mixed latex. Embedded image