JPS62231077A - 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 <Industrial Application Field> The present invention relates to a method for treating polynisnal fibers for rubber reinforcement with improved adhesion to rubber compounds.

<Prior art> Polyester fibers, typified by polyethylene terephthalate fibers, have physical properties such as high strength, Young's modulus, low elongation, low creep, and excellent fatigue resistance. It is widely used for applications such as reinforcing composites.

However, compared to polyamide fibers such as nylon 6 and nylon 6.6, polyester fibers have poor adhesion to rubber materials, and normal adhesive treatment is necessary to fully demonstrate the physical properties of polyester fibers. Strong adhesion performance cannot be obtained. 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 a highly reactive substance such as an epoxy compound or an incyanate compound to impart adhesive properties. (For example, special public service in 1986
-55632 publication,! ! # Publication No. 47-49768 [Japanese Patent No. 692769], etc.) 1. However, when trying to improve the adhesion of polyester fibers to rubber, the treated fiber material becomes hard (and the molding process becomes difficult). In addition to becoming difficult, a problem arises in that fatigue resistance decreases.

<Objective of the Invention> The present invention was made against the background of the above circumstances, and the object of the present invention is to improve the adhesion between polyester fiber number and rubber.5. In particular, the purpose is to provide excellent performance in heat-resistant adhesive properties at ℃.

<Structure of the Invention> That is, the present invention combines linear aromatic polyester fibers with 2,6-dimethyl-4-chlorophenol and a polyepoxide compound (
Pre-treated with a liquid containing Al, and then containing a polyepoxide compound tn+, a pulled polyincyanate compound (C) and a rubber latex Q)).
First treated with a treatment agent, then resorcin, formalin, etc.
An ethylene urea compound represented by the following general formula (E) and an epoxy cresol novolak condensate represented by the following general formula are added to rubber latex (RFL).
A method for treating polyester fibers characterized by treating with a second treating agent added at a weight ratio of 100 to 80/20. - The 2,6-dimethylol-4-chlorophenol used in the pretreatment agent of the present invention [2] is produced at L°C with its intermediate during the reaction of resorcinol, p-riprophenol, and formaldehyde.

Next, the polyepoxide compound used in the pretreatment agent and the first treatment agent of the present invention is a compound containing a small amount (both 2 or more) of epoxy groups in one molecule in an equivalent amount of 0.2 or more per 1002 of the compound, and ethylene glycol. , reaction products of polyhydric alcohols such as glycerol, sorbitol, pentaerythritol, polyethylene glyfur and halogen-containing epoxides such as epichlorohydrin;
Reaction products of polyvalent 7 ethers such as resorcinol/bis(4-hydroxyphenyl)dimethylmethane, phenol/formaldehyde resin, resorcinol/formaldehyde resin and the above halogen-containing epoxides, peracetic acid or hydrogen peroxide Polyepoxide compounds obtained by oxidizing unsaturated compounds with etc., namely 3.4-diboxycyclohexene epoxide, 3.4-epoxycyclohexylmethyl-
Examples include 3,4-epoxycyclohexenecarboxylate and bis(3,4-epoxy-6-methyl-cyclohexylmethyl)7dibate. 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 a polyepoxide compound is usually preferably used in combination with an emulsion.

To make an emulsion or solution, for example, the polyepoxide compound may be dissolved as it is or if necessary in a small amount of a solvent, and then mixed with a known emulsifier such as alkylbenzenesulfonic acid, dioctyl sulfosuccinate sodium salt, Emulsify or dissolve using nonylphenol ethylene oxide adduct.

Next, the blocked polyisocyanate compound used in the first treatment agent of the present invention is an addition compound of a polyisocyanate compound and a blocking agent, and a pull component is liberated by heating to produce an active polyisocyanate compound. be. The polyincyanate compound is, for example, tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate.

Polyisocyanates such as polymethylene polyphenylinocyanate and triphenylmethane triisocyanate, or compounds having two or more active hydrogen atoms with these polyisocyanates, such as hatrich p-leupane, pentaerythritol, etc., can be combined with incyanate groups (-NGO
Examples include polyalkylene glycol adduct polyisocyanates containing terminal incyanate groups obtained by reacting at a molar ratio of 1) and hydroxyl groups (-()H) exceeding 1. In particular, aromatic polyincyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenylinocyanate are preferred because they exhibit excellent performance.

As a blocking agent, for example phenol.

Phenols such as thiophenol, cresol, and resorcinol; aromatic secondary amines such as diphenylamine and xylidine; lactams such as phthalic acid imides; caprolactam and valerolactam; oximes such as acetoxime, methyl ethyl ketone oxime, and cyclohexane oxime; Examples include acidic sodium sulfite.

Examples of the rubber latex used in the first treatment agent of the present invention include natural rubber latex, styrene butadiene,
Copolymer latex, vinylpyridine-styrene-butadiene terpolymer latex, nitrile rubber latex.

There are chloroprene rubber latex, etc., and these can be used alone or in combination. Among these, vinylpyridine
Excellent performance is shown when styrene-getadiene-terpolymer latex is used alone or when 1/2ik or more is used.

The pretreatment agent has a blending weight ratio of the above-mentioned 2,6-dimethyl-4-chlorophenol and the polyepoxide compound (total).
It is preferable to use (A)/2,6-dimethyl-4-trifluoride.

The first treatment agent is the above polyepoxide compound CB).

Contains blocked polyincyanate compound C) and rubber latex (D) (B), tC), ■) The ratio of each component to blend type 1 is a3)/C(Bl+(C)) is 0.0
5-0.9, Cl+/[Ta1-HQ] is 0.5-15
It is preferable to set it to 5 and use it. Special Ni(E>/
((B++(C)) 0.1~0.5, ■/(
It is preferable to blend so that (B) + (C) ) is in the range of 1 to 10 (-I, where 03)/[(B) +
If (Q) is outside the above range, the rate of rubber adhesion to polyester fibers tends to be poor and the adhesiveness tends to decrease, and if (■)/[D)+(C)) is smaller than the above range, processing will be carried out. [5] Polyester fibers that are thicker than the above range may become stiff, leading to a decrease in fatigue resistance.
If this happens, the adhesion will decrease (, te(ro).

Polyexito compound (B), blocked polyisocyanate compound (C1 and rubber latex ■)'? : The total solid content concentration is 1 to 30 wt%, preferably 3 to 20 wt%, based on the fiber weight. If the concentration is too low, the adhesion will decrease, and if the concentration is too high, it will become hard (
Therefore, fatigue resistance decreases.

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 it exceeds the above range, the adhesiveness tends to decrease slightly. It is in.

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 1:01 to 1:1. 8. Preferable 1. (is 1
:05 to 1:5, more preferably 1:1 to 1:4.

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

Among these, vinylpyridine/styrene/getadiene/terpolymer latex shows excellent performance when used alone or when used in an amount of 1/2 or more.

The blending ratio depends on the addition ratio of the ethylene urea compound [F]) and the epoxy-modified phenol/formalin resin condensate n, which will be described later, but the solid content ratio is 1:1 to 1:1.
5. Preferably, the ratio is in the range of 1:3 to 1:12. If the ratio of rubber latex is too small, the treated polyester fiber material will become hard and its fatigue resistance will be poor.

On the other hand, if it is too large, the desired adhesive strength and rubber adhesion rate cannot be obtained.

The mixing ratio of the urea compound [F]) and the epoxy-modified phenol formalin condensate F) is 50150~
so/2o (it ratio) is preferred, and the mixture is
0.5 to 30 vtl, preferably 1.0 to LK
20 wt. If the amount of the mixture added is too small, good adhesion and rubber adhesion cannot be obtained. On the other hand, if the amount added is too large, the viscosity of the treatment agent increases significantly, making it difficult to process the fiber material.Furthermore, the adhesive strength and rubber adhesion rate may differ from the saturation value, making it difficult to control the amount of the mixture added. However, the effect is not improved, the cost only increases, and the fiber material after treatment becomes extremely hard (and its strength decreases).

The ethylene urea compound added to the second treatment agent is represented by the following general formula E).

Typical compounds include octadecyl isocyanate and hexamethylene diinocyanate.

Isophorone diisocyanate, tolylene diisocyanate, metaxylene diisocyanate.

Examples include reaction products of aromatic or aliphatic incyanates such as diphenylmethane diisocyanate, naphthylene diisocyanate, and triphenylmethane triisocyanate with ethylene sulfur, and aromatic ethylene urea compounds such as diphenylmethane diethylene urea have shown particularly good results. give.

Same (epoxy-modified phenol added to the second treatment agent)
The formalin condensate has the following general formula % Formula % Various compounds can be considered that satisfy the above (F').
q/Ni gives good results.

In the present invention, the ethylene urea compound (provided) and the epoxy-modified phenol/formalin condensate (g) have a catalytic effect on each other, and the ethylene urea compound has an ethylene imine ring opened, and the epoxy-modified phenol/formalin condensate In this case, the epoxy ring undergoes a ring-opening reaction, which improves adhesiveness and at the same time increases the cohesive force of the adhesive itself.As a result, it forms a strong chemical bond with the amines generated in the rubber.
This prevents adhesive deterioration.

The above-mentioned second processing agent is usually adjusted to have a solid content of tlo to 25% by weight.

The first treatment agent and the second treatment agent (t) K to be attached to the polyester fiber material also comes into contact with p-lar. Any method can be employed, such as application by spraying from a pouring nozzle or immersion in a solution. Polyester Am miscellaneous 2't
The amount of solid content adhered to the first treatment agent composition is 0.1 to ℃.
10 times, f! t%, preferably (, (is 0.5 to 5% by weight, preferably 0.5 to 1oIH1%, preferably 1 to 5% by weight) with the second treatment agent composition. In order to control the amount of solid content attached to the fibers, squeezing with a pressure roller, scraping off with a souffle bar, etc.

Blow-off by air blowing (-1 suction, beating with a beater, etc.) may also be used.

In the present invention, 2,6-dimethyl-4-diI:
After pretreatment with a treatment solution containing lp phenol and a polyepoxide compound, drying and heat treatment at a temperature of 160°C or higher and 10°C or more lower than the melting point of the polyester fiber, followed by treatment with a first treatment agent and then a temperature of 50°C or higher to form the polyester fiber. is a temperature 10°C or more lower than the melting point of the fiber, preferably 220 to 250°C.
The polyester fibers are dried and heat treated at a temperature of 120°C or above and below the melting point of the polyester fiber, preferably 18°C to 250°C. If the drying/heat treatment temperature is too low, the adhesion to the rubber will be insufficient, while if the temperature is too high, the polyester fibers will melt.

This may cause fusion t5 or a significant decrease in strength, making it unusable for practical use.

<Effects of the invention> Compared to the conventional method, the fibers treated by the method of the present invention have
Improved heat-resistant adhesion (and improved peel strength and durability) without impairing processability with rubber.

<Example> Hereinafter, the present invention will be explained in terms of a tool using examples.

In addition, in the examples, the rubber intermediate thermal properties, hood peeling adhesive strength, T adhesive strength, and interbraid peeling force are values obtained by L7 as follows.

<Heat resistance in rubber> This indicates the strength retention rate after vulcanization in rubber. After vulcanization in the rubber at 170° C. for 3 hours, the cord was taken out from the rubber, and the tensile strength at break was determined at a speed of 200 m/m, and the retention rate was determined in comparison with the initial strength.

<Cord peeling adhesive strength> Indicates the adhesive strength between the processing hood and rubber. Five hoods were buried near the surface of the COM sheet, 150℃ under pressure,
After 30 minutes of vulcanization, 5 lines (T adhesive strength) indicate the adhesive strength between the treated cord and the rubber. The hood was embedded in a rubber block and heated at 150℃ for 30 minutes under pressure.
200 m/min from the rubber block.
Pull it out at the speed of jElil, and the force required to pull it out is Ky.
Displayed in cm.

<Peeling force between plies> Treatment=+ - Indicates the adhesive strength with After vulcanizing the rubber at 150°C for 30 minutes, both plies were heated to 200 tons.
Force required for peeling at a tensile speed of tIR/m 1:
It is expressed in kg/1nch.

<Rubber adhesion rate> This is a measure of the adhesion of rubber to fibers.

During the above-mentioned σ-knobli peel force measurement, the cord that was peeled off from the rubber was observed with the naked eye.
．． 1. Display the percentage as a percentage. It is something that

Examples 1-3. Comparative Examples 1 to 6 20
wt% ammonia aqueous solution 100PK Denacol @ EX
-ci 11 (Nagaushio Sangyo @N, Tsuru?) -polyglycidyl ether) 6F/℃ surfactant and 17℃
, Neocol ■ 5W-30 (manufactured by Daiichi Kogyo Seiyaku ■, dioctylsul7-osuccinate sodium) This is added to water 8052 with stirring, and Bunafur ■ EX-611 is uniformly dissolved in water. Next, Hiren ■MP (1177 phenols of 4.4-diphenylmethane diisocyanate in DuPont ■!1) 149. Neocol ■5W-
A dispersion obtained by mixing 30,4F and water 422 in a ball mill for 24 hours and Ninopol ■2518FS (
Add 125% of a 40% water emulsion of vinylpyridine/styrene/butadiene terpolymer (manufactured by Nippon Zeon) and mix uniformly. The obtained liquid mixture is used as a first treatment agent.

In addition, 10% caustic soda aqueous solution 10F and 28% thiammonia aqueous solution 302 were added to water 2601 and stirred well. C Into the obtained aqueous solution, react with an acidic catalyst f, and add the initial condensate of resorcinol/formalin (40% acetone solution) 60
1]- to sufficiently stir and disperse. Next, Nilaball ■2518GL (manufactured by Nippon Zeon ■, vinylpyridine,
Styrene-butadiene-terpolymer latex 40%
water emulsion) 240F and Nilapol ■LX'-112 (
Made by Nippon Zeon ■, Styrene Getadiene Copolymer 4
Dilute 0.0 ml of water emulsion) with 200 ml of water. The resorcinol/formalin initial condensation dispersion was slowly added to this diluted solution while stirring, and then formalin (37% aqueous solution) 20F was added and mixed uniformly. Next, diphenylmethane diethylene urea 14F**Ofur 5W-3051 and 36 ml of water were stirred and mixed in a ball mill for 24 hours to this mixed solution, and the resulting aqueous dispersion was added and mixed. Next, ECN1299 (phenol/formalin resin cotton hardware epoxy compound manufactured by Ciba Geigy) 7.21 was dissolved in toluene in advance, and Neocol ■P (manufactured by Daiichi Kogyo Seiyaku ■, dioctylsulfosuccinate sodium salt) 0. Add IP and methyl cellulose 0.6 F, dissolve at ℃, add to the prepared aqueous solution 281 with stirring, and add the dispersed product to mix 11, and use the resulting mixed solution ft[2 as a processing agent.

Polyethylene terephthalate with C-rB = O, 11+9 was melt-spun and drawn according to a conventional method to obtain a multifilament of 1500 denier/L-/192 filament, and then the two multifilaments were divided into 40×40
T/10 twist yarn was used to obtain a 3000 denier/384 filament cord. The above cord is pre-soaked in a pre-treatment agent and then heat-treated at 180°C for 3 minutes in a food processing machine.
.

These Food Manufactured Funpy Treater [F] processing machines (
After being immersed in the first treatment agent at 150°C using a tire cord processing machine (manufactured by CA Ritzler ■), it was dried at 150°C for 2 minutes, and then heat-treated at 230°C for 1 minute. Then the second
After being immersed in the treatment agent for 1°, it is dried at 150°C for 2 minutes and then heat treated at 230°C for 1 minute. The treated polyester tire cord had a solid content of 2.2 wt% of the first treatment agent.

A solid content of 2.5 wt % of the second treatment agent was adhered.

The treated cord thus obtained was embedded in unvulcanized rubber containing a carcass containing natural rubber as the main component, and heated at 150°C for 3 hours.
0 minutes (initial value) and 170°C, 90 minutes (heat resistance value) vulcanization 1. Ta.

As shown in Table 1, the above experiment was carried out using 2,6-dimethylol-
The process was repeated by variously changing the weight ratio of 4-riqa7 ether to the polyepoxide compound and the weight ratio of the compound to the epoxy-modified phenol/formalin condensate.

The experimental results are shown in Table 1.

Claims (1)

[Claims] (1) A linear aromatic polyester fiber pretreated with a treatment solution containing 2,6-dimethylol-4-chlorophenol and a polyepoxide compound (A) is treated with a polyepoxide compound (B) and a blocked polyisocyanate compound (C). ) and rubber latex (D), and then resorcin formalin rubber latex (RFL) is treated with an ethylene urea compound represented by the following general formula (E) and the following general formula [F]. Epoxy cresol novolac condensate (E)/(F)=2
Polyester fiber processing method characterized by treatment with a second processing agent added at a weight ratio of 0/80 to 80/20 ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (E) [Here R is aromatic or aliphatic hydrocarbon residue, n is 0
, 1 or 2. When n=0, the terminal group is hydrogen. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼(F) [Here, R' is -O-(CH_2)-_kCl, -O-
(CH_2)-_lOH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R'' is -H, -CH_3, -C_2H_5
k, l, m are integers of 1 to 4, m' is an integer of 1 to 5, a, b are integers of 1 to 5, and a+b≦
It is 6. ]