JPS6297977A - 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 Field of 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 fibers and rubber. We are busy providing processing methods.

In particular, the present invention focuses on the rate of rubber adhesion to polyester fibers (Ru
The present invention relates to a processing method for improving polyester fibers (bbor coverage) and making polyester fibers flexible and excellent in fatigue resistance.

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

[5 However, polyester fibers have poor adhesion with °C rubbers compared to polyamide fibers such as nylon 6 and nylon 6/6 (normal adhesive treatment does not sufficiently improve the physical properties of the polyester fibers). It is not possible to obtain the strong adhesion performance necessary to achieve the desired performance.

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, new problems arise in that the treated fiber material becomes hard, making molding difficult and reducing fatigue resistance.

<Invention σ>Purpose> 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,
In particular, it is intended to provide heat-resistant adhesive odor control and excellent performance.

To achieve this purpose, polyester ti! The present invention was developed as a treatment method for imparting adhesion between fibers and rubber, particularly excellent heat-resistant adhesion.

<Structure of the Invention> That is, the present invention provides a linear aromatic polyester fiber t resorcinol formalin rubber latex (RF'
L) is an ethylene urea compound represented by the following general formula (4) and an epoxy-modified phenol/formalin condensate represented by the following general formula CB+ at a weight ratio of (4)/[F]) of 50150 to 80/20. This is a method for treating polyester fibers, which is characterized by treating polyester fibers with a treatment agent mixed within the following range.

The present invention can be applied to any type of linear aromatic polyester, and polyesters having one unit as a main component are preferred, even if they are represented by the general formula (n' is an integer of 2 to 6). Polyesters containing at least one type of glycol selected from ethylene glycol and tetramethylene glycol as a main glycol component are preferably used. Molecular weight of polyester fibers.

It goes without saying that the denier, number of filaments, cross-sectional shape, fiber properties, microstructure, presence or absence of additives, and polymer properties (terminal carboxyl group concentration, etc.) are not limited in any way.

The epoxy compound to be pretreated on the linear aromatic polyester of the present invention is a compound containing a small amount (both 2 or more epoxy groups) in an amount of 082?equivalent or more per 1OOf of the compound, such as ethylene glycol, glycerol, or sorbitol.

Resorcinol bis(4
-Hydroxyphenyl)methylmethane, phenol
Polyepoxide compounds obtained by oxidizing unsaturated compounds with peracetic acid, hydrogen peroxide, etc., reaction products of polyhydric phenols such as formaldehyde resins, resorcinol/formaldehyde resins, and the above halogen-containing epoxides, i.e., 3,4 -Epoxycyclohexene epoxide, 3,4-
Examples include epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate and bis(3,4-epoxy-6-methyl-cyclohexylmethyl)7dibate.

Such an epoxide compound is usually preferably used with an emulsion at 0°C. To make an emulsion or solution, for example, such a polyepoxide compound as it is or dissolved in a small amount of solvent as necessary is mixed with a known emulsifier such as sodium chloride benzenesulfonate, dioctyl sulfosuccinate sodium salt, Emulsify or dissolve using nonylphenol ethylene oxide adduct.

When applying such an epoxy compound-containing emulsion to M fibers, it is mixed with a conventionally known fiber smoothing agent.
It is preferable to use ``''C.

Textile smoothing agent and L t are mineral oil, higher fatty acid and higher alcohol σ-noester 2. For example, butyl stearate,
oleyl laurate, isostearyl palmitate, oleyl oleate) 2 [ester of base liquid and higher alcohol,
For example, dioctyl sebacate, dioctyl azelate,
Esters of trihydric alcohols and higher fatty acids such as dioleyl adipate, aliphatic esters such as glycerin triolate and trimethylol pudivan tridecanate with molecular % of 300 to 500 are preferably used. Be it.

For the surface treatment agent and L″C, consideration must be given to those that will adhere to the fibers under spinning conditions.For example, for treatment agents containing epoxy compounds, 50 to 90% by weight of glycerin triglycidyl ether, a glycidyl ether compound of raw wood, and a hardening agent. A surface treatment agent containing 1 to 10% by weight of an aliphatic amine such as hexamethylene diamine or viverane with L- and an emulsifier or a general fiber oil is suitable.

By pre-treating the polyester fiber with an epoxy compound containing two or more epoxy groups and leaving it at ℃, the heat setting during the warping process can provide the surface treatment agent necessary for fixation, and as a result, the fiber Because surface modification is effectively carried out, when treated with a second treatment agent containing epoxy-modified phenol/formalin condensate, it exhibits sufficient cracking and reactivity, resulting in improved heat-resistant adhesion at high temperatures. I think that the.

The processing 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 the molar ratio of resorcinol and formaldehyde is Crab 01-1:8, preferably 1:0,5-
The ratio is preferably 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, gloloprene rubber latex, etc., and these can be used alone or in combination.

Among these, the use of vinylpyridine/ethylene/butadiene terpolymer latex alone or in an amount of 1/2 or more shows excellent performance.

The blending ratio of resorcinol/formalin and rubber latex is the ethylene urea compound (5) described below.

It also depends on the addition ratio of epoxy-modified phenol/formalin resin condensate), but the solid content ratio is 1:1 to 1:1.
15. Preferably, the ratio is in the range of 1:3 to 1:12. If the ratio of rubber latex is too low, the treated polyester fiber material becomes hard (and fatigue resistance deteriorates).On the other hand, if it is too high, satisfactory adhesive strength and rubber adhesion rate cannot be obtained due to the formation of urea compound particles. The mixing ratio of epoxy-modified phenol/formalin condensate) is 50150 to 80/2.
0 (weight ratio) is preferable [2 (, the mixture has the above RFL
K i L, 0.5-30 vt%, preferred [, < is 1.
0-20 vtqb added. 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 processing agent will increase significantly, making it difficult to process the fiber material. Moreover, adhesive strength,
If the rubber adhesion rate is different from the saturation value, increase the amount of the mixture added.
However, the effect is not improved and the cost increases, and the fiber material after treatment becomes extremely hard and has a reduced strength, resulting in a shortcoming.

Typical ethylene urea compounds are those represented by the following general formula (3), such as octadecyl isocyanate and hexamethylene diinocyanate.

Isophorone diisocyanate, tolylene diisocyanate, metaxylene diisocyanate.

Examples include reaction products of aromatic or aliphatic incyanates such as diphenylmethane diincyanate, naphthylene isocyanate, triphenylmethane triincyanate, and ethyleneimine, particularly aromatic ethylene urea compounds such as diphenylmethane diethylene urea. gives good results.

The epoxy-modified phenol/formalin condensate is represented by the following general formula (). Various compounds can be considered that satisfy the above formula B, but the molecular weight is 1200 to 130.
0 and an epoxy value of 4.0 to 4.5"t,/Kf gives good results.

In the present invention q, the ethylene urea compound (2) and the epoxy-modified phenol/formalin condensate) have a catalytic effect on each other, and the ethylene urea compound causes the ethyleneimine ring to open, and also causes the epoxy-modified phenol/formalin condensation to occur. In the product, the epoxy ring undergoes a ring-opening reaction (-) which increases the adhesion and at the same time increases the cohesive force of the adhesive itself.As a result, the 7ξn species generated in the rubber form a chemical oxidation that is strong at 11℃. This prevents adhesive deterioration.

The above-mentioned processing agent is usually adjusted to contain 10 to 25% by weight of solids.

In order to adhere the treatment agent to the polyester fiber material, contact with a roller is also required in 1. Any method can be used, such as application by spraying from a nozzle or immersion in a bath solution. The amount of solid content deposited on the polynisder fiber is 4 to 10% by weight, preferably 1. < is preferably 5 to 8 weight. In order to control the amount of solid matter adhering to the fibers, means such as squeezing with a pressure roller, scraping off with a souffle bar, blowing off with an air blower, suction, and beating with a beater may be used.

In the present invention, a molten polyester polymer is extruded from a spinneret, a surface treatment agent containing an epoxy compound is applied using, for example, an oiling roller, and then stretched and heat-set.

A leveling agent or a mixture of a leveling agent and a surfactant is then applied. Stretching and heat setting are usually carried out at 80°C to 260°C for about 0.1 to 5 seconds.

The fibers thus obtained may be twisted to form a ℃ cord.
The paper is bound and treated with a processing agent to remove stains.

This treatment is carried out by drying and heat treatment at a temperature of 120°C or higher and lower than the melting point of the polyester fiber, preferably 180 to 250°C. If the drying/heat treatment temperature is too low, the adhesion with the rubber will be insufficient, while if the temperature is too high, the polyester fiber will melt.

It may cause 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
Improves heat-resistant adhesion (and improves peel strength and durability) without impairing processability with rubber.

<Example> Hereinafter, the present invention will be explained with reference to examples.

In addition, in the examples, the thermal properties of the rubber, the cord peeling adhesive strength, the T adhesive strength, and the interbraid peeling force are as follows: Kl, 'C
This is the obtained value.

<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, the tensile strength at break was determined at a rate of 200 vm/wllI, and the retention rate was determined by comparing it with the initial strength.

<Cord peeling**Adhesion strength> Indicates the adhesive strength between the treated cord and rubber.Fill 5 cords near the surface layer of the rubber sheet and peel under pressure at 150°C.
, 30 minutes of vulcanization, then 5 cords from the rubber sheet 2
The force required for peeling at a speed of 00 cm/m is expressed in Kf15.

<T adhesive strength> This indicates the adhesive strength between the processing hood and rubber. Embed the cord in a rubber tube and heat it at 150℃ for 30 minutes under pressure.
Vulcanize for 20 minutes, then remove the cord from the rubber boot stock for 200cm/
Pull it out at a speed of i, and the force required to pull it out is Kf/cm
This is what is displayed.

<Peeling force between plies> This indicates the adhesive force with the processing hood. Embed 2-ply processed cords in the rubber at a 90 degree angle as a tuxply (cord density: 27 cords/inch)15
After vulcanization at 0'C for 30 minutes, both brakes were vulcanized at 200cm/m.
The force required to peel off at a tensile speed of lI is KW /
It is displayed in 1 nch.

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

During the above inter-ply peel force measurement, the cord that was peeled off from the rubber was observed with the naked eye.
Example 1. Comparative Example 1 Polyethylene terephthalate of 1i=o, s9 was prepared by a conventional method (
Therefore #! Melt spinning, stretching 1500 denier/192
After obtaining the filament multifilament, the two multifilaments were then twisted and twisted for 4 times each.
A cord of 3000 denier/384 filament was obtained by twisting at 0T710m. Attached table IK during spinning or drawing
After treatment with the indicated surface treatment agent, it was heat-set at 200C for 2.5 seconds.

The treatment agent for the epoxy pre-treated polyester fibers is IO'% caustic soda aqueous solution 102.28 thiammonia aqueous solution 3 of water is added to 260 PK of water, stirred well, and the resulting aqueous solution is reacted with an acidic catalyst for initial condensation of resorcinol/formalin. Add 6 of P (40% thiacetone solution) and stir thoroughly to disperse C1. Next, leek ball ■25
18GL (vinyl pyridine styrene manufactured by Nippon Zeon)
butadient terpolymer latex 40% water emulsion) 2
40? and Nilaball Co., Ltd. Lx-112 (manufactured by Nippon Zeon, 40% water emulsion of styrene getadiene copolymer) 100F was diluted with water 2002. Add the above-mentioned resorcin-formalin initial condensation dispersion to this diluted solution while stirring and bring to 10°C, then add formalin (37% aqueous solution) 2 (MF) and mix uniformly.

Next, add 1/7 diphenylmethane to this mixture.
R element 14 f * t Cole ■5W-30 (manufactured by #E-Kogyo Seiyaku ■, dioctylsulfosuccinate sodium salt 30% aqueous solution) 5f and water 362 were mixed in a ball mill for 2
The aqueous dispersion obtained by stirring and mixing for 4 hours at °C is added and mixed.

Next, ECN1299 (manufactured by Ciba Geigy ■, epoxy compound of phenol-form resin condensate) 7
．． After preliminarily dissolving 2f in toluene, 0.1 t of Neocol ■P (manufactured by Daiichi Kogyo Seiyaku ■, dioctyl sulfosuccinate sodium salt) and 0 methyl celtose were added.
．． 6t and water 281 with stirring C-, and the resulting mixture is added and mixed (-1) The resulting mixed liquid is used as a processing agent.

A cord made of epoxy-pretreated polyester fibers prepared in advance was dipped in the treatment agent using a Conbutreta 20 treatment machine (tire cord treatment machine manufactured by CA Ritzler@), and then dried at 150°C for 2 minutes. Then, heat treatment was performed at 240° C. for 1 minute.The adhesion rate was determined to be 1.6%, and 6.0% solid content of the treatment agent was adhered to the treated polyester tire cord.

The treated cord thus obtained was embedded in an unvulcanized rubber compounded with a carcass containing natural rubber as a main component, and was heated to 150'0.
30 minutes and 170°C.

Vulcanized for 90 minutes. Each condition corresponds to the initial value and heat resistance value in Table 2, respectively.

As shown in Table 2, the above experiment was carried out using ethylene urea compound (2).
The procedure was repeated by variously changing the weight ratio of and epoxy-modified phenol/formalin condensate (B).

The experimental results are shown in Table 2.

Table 1 (Units are parts by weight)

Claims (1)

[Claims] (1) Linear aromatic polyester fibers previously treated with an epoxy compound containing two or more epoxy groups are mixed with resorcinol-formalin-rubber latex (RFL) and an ethylene urea compound represented by the following general formula (A). The weight ratio of (A)/(B) is 50/50 with the epoxy-modified phenol/formalin condensate represented by general formula (B).
Processing method for polyester fiber characterized by treatment with a treatment agent mixed in the range of ~80/20▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(A) [Here, R is aromatic or an 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.▼・・・・・・(B) [Here, R' is -O-(CH_2)_k-Cl, -O-
(CH_2)_l-OH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R'' is either H, CH_2, C_2H_3, k, l, m are integers from 1 to 4, m' is from 1 to 5 The integers a and b are integers from 1 to 5, and A+b≦6.