JPS6099073A - Treatment of polyester fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for treating polyester fibers, and its purpose is to produce polyester fibers that have dramatically improved heat-resistant adhesion between the twill fibers and rubber. The purpose is to provide a processing method.

In particular, the present invention provides a rubber adhesion rate (R
The present invention relates to a processing method for improving the fibercoverage of polyester fibers and making polyester fibers flexible and excellent in fatigue resistance.

Prior Art Polyester fibers, represented by polyethylene terephthalate fibers, have physical properties such as strength, high Young's modulus, low elongation, low creep, and excellent fatigue resistance, and are suitable for rubber reinforcement composites. It is widely used for such purposes.

However, polyester fibers have poor adhesion to rubber compared to polyamide fibers such as nylon 6 and nylon 6/6, and ordinary adhesive treatment is not necessary to fully demonstrate the physical properties of polyester fibers. Strong adhesion performance cannot be obtained due to sand. The main reason for this is thought to be that the hydrogen bonding capacity of ester bonds in polyester is smaller than that of amide bonds in nylon. For this reason, a method has been proposed in which the surface of polyester fibers is treated with highly reactive substances such as epoxy compounds and incyanate compounds to impart adhesive properties.

However, when trying to improve the adhesion of polyester fibers to rubber, the treated fiber material becomes hard and
New problems arise in that molding becomes difficult and fatigue resistance decreases.

Purpose of the Invention The present invention was made against the background of the above circumstances, and the purpose of the present invention is to improve the adhesion between polyester fiber and rubber,
We are working hard to provide excellent performance, especially in heat-resistant adhesion.

In order to achieve this object, the present invention has been devised as a treatment method for imparting adhesive properties, particularly excellent heat-resistant adhesive properties, between polyester fibers and rubbers.

Structure of the Invention Namely, the present invention provides polyepoxide compounds and hismaleimide derivatives in a mixing ratio (A/B of IA to 1/1).
This is a method for treating polyester fibers, which comprises treating with a first treating agent containing a resorcinol-pormarine rubber latex, and then treating with a second treating agent containing a resorcinol-polmarine rubber latex.

The present invention can be applied to any linear aromatic polyester K, and in particular, polyesters whose main constituents are repeating units represented by the general formula (n' is an integer of 2 to 6) are preferably used, and particularly A polyester whose main glycol component is at least one type of glycol selected from ethylene glycol and tetramethylene glycol is preferably used. Polyester fiber molecular weight, denier, number of filaments, cross-sectional shape, fiber physical properties,
It goes without saying that there are no limitations on the microstructure, the presence or absence of additives, and the polymer properties (terminal carboxyl group porosity, etc.).

The polyepoxide compound used in the first treatment agent of the present invention has at least two or more epoxy groups in one molecule. It is a compound containing 0.23 equivalent or more per 100 ml, and is a reaction product of polyhydric alcohols such as ethylene glycol, glyce-p-leusorbitol, pentaerythritol, and polyethylene glycol and halogen-containing epoxides such as epichlorohydrin, resorcinol, etc. Reaction products of polyhydric phenols such as bis(4-hydroxyphenyl)dimethylmethane, phenol-formaldehyde resins, and resoln-formaldehyde resins with the above-mentioned halogen-containing epoxides, unsaturated compounds with peracetic acid or hydrogen peroxide, etc. Polyepoxy compound obtained by oxidation, namely 3,4-epoxycyclohexene epoxide, 3
, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate, and the like. Among these, reaction products of polyhydric alcohols and epichlorohydrin, ie, polyglycidyl ether compounds of polyhydric alcohols, are particularly preferred because they exhibit excellent performance. Such polyepoxide compounds are usually used as emulsions or solutions. K to be made into an emulsion or solution is, for example, such a polyepoxide compound as it is or dissolved in a small amount of solvent as required, with known emulsifiers such as sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol. Emulsify or dissolve using ethylene oxide adduct, etc.

The bismaleimide conductor used in the first treatment agent of the present invention contains two or more maleimide groups in its molecule, and m-phenylene bismaleimide is the best known, but it is not limited to this. It's not something you can do. The amount of bismaleimide derivative used is 1% per polyepoxide compound.
72~1/1! It shows excellent performance when used.

The total solid concentration including the polyepoxide compound and bismaleimide derivative is 1 to 30 wt%, preferably 3 to 20 wt% IIC based on the weight of the fiber. If the concentration is too low, the adhesion will decrease, and if the concentration is too high, it will become hard and the fatigue resistance will decrease.

A dispersant when using the first treatment composition as an aqueous dispersion,
That is, an appropriate amount of the surfactant is 0 to 15 wt %, preferably 10 wt % or less, based on the total solid content of the first treatment agent, and if the amount exceeds the above range, the adhesiveness tends to decrease slightly.

The second treatment agent of the present invention is a composition containing resorcinol/formalin/rubber latex, and the resorcinol/formalin/rubber latex used here is usually called RFL, and is a composition containing resorcinol/formalin/rubber latex. The molar ratio of the aldehyde is 1:o, l~l28, preferably l:0
．． It is used in a range of 5 to 1:5, more preferably 1:1 to 1:4.

Examples of rubber latex include natural rubber latex,
There are styrene-butadiene-fupolymer latex, vinylpyridine-styrene-butadiene terpolymer latex, nitrile rubber latex, polypropylene rubber latex, etc., and these can be used alone or in combination.

Among these, the use of vinylpyridine/styrene/styrene/styrene/terpolymer latex alone or in an amount of 172 or more shows excellent performance.

The blending ratio of resorcinol/formalin and rubber latex is l=1 to 1:1s in solid weight ratio, preferably tL<i! x
: 3 to 1 : 12 (1) It is desirable to have BK in the range.

If the proportion of rubber latex is too small, the treated polyester fiber material will become hard and have poor fatigue resistance. On the other hand, if the amount is too large, satisfactory adhesive strength and rubber adhesion rate cannot be obtained.

The bismaleimide derivative conductor used in the present invention is efficient if it contains two or more maleimide groups in the molecule. For example, etc.

In the present invention, the bismaleimide derivative exhibits strong adhesive strength by reacting with the double bonds in the rubber latex or the double bonds in the rubber in the second treatment agent.

The above-mentioned second processing agent usually contains 10 to 25 mff1 of solid content.
w4 is adjusted to contain %.

In order to attach the first treatment agent and the second treatment agent to the polyester fiber material, any method such as contact with p-lar, application by spraying from a nozzle, or immersion in a solution can be adopted. The amount of solid content deposited on the polyester fiber is 0.1 to 10% by weight for the first treatment agent composition, preferably 0.5 to 5% by weight for the second treatment agent composition, and 0.5 to 10% by weight for the second treatment agent composition. ft., preferably 1 to 5 ft. by weight. In order to control the amount of solid content attached to the fibers, squeezing with a pressure welding p-ler, scraping off with a souffle bar, etc., blowing off with air blowing,
Means such as suction and beating with a beater may also be used.

In the present invention, after treating the polyester green fiber with the first treatment agent, it is dried at a temperature of 50°C or higher and 10°C or more lower than the melting point of the polyester fiber, preferably at a temperature of 220 to 250°C.

Heat-treated and then treated with a second treatment agent to achieve a temperature of 120°C or higher and lower than the melting point of the shark polyester fiber, preferably 1
Drying and heat treatment at a temperature of 80 to 250°C. If the drying and heat treatment temperature is too low, the adhesion with the rubber will be insufficient, while if the temperature is too high, the polyester fibers will melt and fuse, and the strength will be significantly reduced, making it impossible to put it into practical use. .

Effects of the Invention The FC ML M treated by the method of the present invention has improved heat-resistant adhesion and improved peel strength and durability compared to conventional adhesives without impairing moldability with rubber.

Example Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, in the examples, heat resistance in rubber, CRA adhesive strength, T
The adhesive strength and inter-ply peel strength were determined as follows.

<Heat resistance in rubber> Indicates the strong retention rate of heat removal in rubber. After vulcanization in rubber at 170"C for 3 hours and 8 hours, a more cordial lubrication was achieved in the rubber, the tensile strength at break was measured at a rate of 2 ooms/min, and the retention rate was measured in comparison with the initial strength of 1.

CRA Adhesive Strength> Indicates the adhesive strength between the treated cord and rubber. Bury 5 hoods near the rubber sheet surface 1 and heat to 150℃ under pressure.
, 30 minutes of vulcanization, then 5 cords from the rubber sheet 2
The number of hexagonal lines required for M peeling (peeling at a speed of 0ON/-) is expressed as 15 lines.

<T adhesive strength> This indicates the adhesive strength between the treated cord and rubber. The coat was embedded in a rubber block and heated at 150℃ for 30 minutes under pressure.
Vulcanize the cord for 200s+ from the rubber pull.
Pull it out at a speed of i+/i, and the force required to pull it out is kg/
It is expressed in ctn.

<Peeling force between briars> This indicates the adhesion force with treated cords. The treated cords of 02 briers are embedded in the rubber at a 90 degree angle as p-sply (cord density 27 pieces/inch) 15
After vulcanization at 0°C for 30 minutes, the force required to peel off both brazes at a tensile rate of 200 f/n is kl? / 1nc
It is expressed as h.

<Rubber adhesion rate> This is a measure of the adhesion of rubber to fibers. The fc cord that was peeled off from the rubber during the above inter-ply peel force measurement was observed with the naked eye, and the portion of the cord surface σ to which rubber was attached is expressed as a percentage.

Examples 1-2. Comparative Examples 1 to 3 Denacono $'EX-s1s (manufactured by Nagashio Sangyo ■, nrubitol polyglycidyl ether) 69 was added as a surfactant to Neo2/Tooth SW-30 (manufactured by M-Koia Pharmaceutical ■, dioctyl sulfosaccharide). Add 4 g of 30% aqueous solution of nate sodium salt and dissolve uniformly. Add this to water 5osJK4'
! Add with stirring to uniformly dissolve Denacono (1) Ex-611 in water.

Furthermore, bismaleimide (reagent grade) 3II is added and mixed uniformly. The obtained liquid mixture is used as a first treatment agent.

Also, 10 I of a 10-strength caustic soda aqueous solution.

Add 30 g of 28% ammonia aqueous solution to 260 g of water and stir well. To the resulting aqueous solution, add 60 g of resorcin formalin initial condensate (40-7 setone solution) reacted with an acidic catalyst and stir thoroughly. disperse. Next = Tsupono Sara 25 te F S (manufactured by Nippon Zeon, vinylpyridine-styrene-butadiene-terpolymer latex 40 water emulsion) 240I and Nippono, @Lx-■z (manufactured by E1 7-on ■, styrene・Butadiene tube copolymer 40 parts water emulsion) 100 JF to 2 parts water
Dilute with 00II. The above-mentioned resorcinol/formalin initial condensate dispersion was added to this diluted solution while stirring slowly, and then 20I of formalin (37% aqueous solution) was added.
Add I and mix evenly.

The obtained liquid mixture is used as a second treatment agent.

[Value after embedding in unvulcanized rubber containing a polyethylene terephthalate carcass with η>=0.89 and vulcanizing at 150°C for 30 minutes.

Heat resistance value: IC embedding 1 in unvulcanized rubber with a carcass containing treated cord as the main component, 150°C, 30°C
Value after vulcanization treatment at 70°C for 90 minutes. 2. Patent Applicant: Teijin Limited 3. Procedural Amendment (November 1983-) Indication Patent Application No. 1984-204961 of the case of the Commissioner of the Patent Office, P.C. Relationship between Patent Applicant 1-11 Minamihonmachi, Higashi-ku, Osaka (300) Representative of Teijin Limited Saebe Okamoto Contents of the amendment in the scope of claims column of the specification subject to the amendment As shown in the attached appendix Claims (1) ) Linear aromatic 7m polyester fibers were treated with polyepoxide compounds ((transfer) and bismaleimide derivatives (kawas).
A method for treating polyester fibers, characterized in that polyester fibers are treated at a mixing ratio (weight) of /A from 1/2 to ]/1.

(2) #j! The aromatic polyester has the general formula ÷oc
%coo(cu,)no+ (n is an integer from 2 to 6) The polyester fiber treatment method according to claim 0 (claim 0), which is a polyester fiber whose main constituent is a repeating unit represented by an integer of 2 to 6 .

Claims (1)

[Claims] ill 477 aromatic polyester fiber, polyepoxide compound (2) and bismalemide derivative (2). A method for treating polyester fibers characterized by treating with a second treatment agent at a mixing ratio of B/A of 1/2 to 1/1 (weight>). (2) The linear aromatic polyester has the general formula (n is 2~
12. The method for treating polyester fibers according to claim 11, which is a polyester whose main constituent is a repeating unit represented by (representing an integer of 6).