JPS62276083A - 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 polyester fibers, and its purpose is to produce polyester fibers that have dramatically improved heat-resistant adhesion between the fibers and rubber. The objective is to provide a processing method for

In particular, the present invention relates to a novel treatment method for improving the adhesion performance between reinforced polyester fibers and rubber when the polyester fiber reinforced rubber composite is used under high load and high temperature conditions.

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

However, compared to polyamide fibers such as nylon 6 and nylon 66, polyester fibers have poor adhesion to rubber, and ordinary adhesive treatments do not provide the necessary strength to fully demonstrate the physical properties of polyester fibers. It is not possible to obtain proper fitting performance. The main reason for this is thought to be that the hydrogen bonding capacity of the ester bonds in polynisder is smaller than the hydrogen bonding capacity of the amide bonds in nylon. For this reason, the surface of polyester fibers is treated with highly reactive compounds such as epoxy compounds and incyanate compounds.
Methods of imparting adhesive properties have been proposed (for example, Japanese Patent Publication No. 641-55632, Japanese Patent Publication No. 47-49768).
(Japanese Patent No. 692769, etc.).

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

<Objective of the Invention> The present invention has been made against the background of the above-mentioned circumstances, and an object of the present invention is to improve the adhesion between polyester fibers and rubbers, particularly in terms of heat-resistant doping properties. There are many things that can be granted.

<Structure of the Invention> That is, the present invention provides: (1) Treating a linear aromatic polyester fiber with a pretreatment agent containing a cresol novolak type epoxy compound represented by the following general formula and water-soluble nylon (Bl),
Next, it is treated with a first treatment agent containing a polyepoxide compound (0), a blocked polyisocyanate compound (L and rubber latex), and then the following general formula (
Ethylene urea compound represented by F) and the above-mentioned cresol novolac type epoxy compound (kJ travl /
(A method for treating polyester fibers, characterized by treating with a second treating agent added at a weight ratio of AJ = 40/6o to 80/20.

・・・・・・・・・・・・(A) The present invention can be applied to any linear aromatic polyester, and in particular, the general formula (n is a number from 2 to 6!) A polyester having the recurring unit shown as a main constituent is preferably used, and particularly a polyester having one or more glycols selected from ethylene glycol and tetramethylene glycol as a main glycol component is preferably used.

The cresol novolac type epoxy compound used in the pre-treatment agent and second treatment agent for polyester fibers of the present invention can be considered to satisfy the following general formula (% formula %). , epoxy value 4.0-4.52
The one using 9 for i/ gives good results.

Next, the water-soluble methyl nylon (Bl) used in the pretreatment agent of the present invention is made by adding and polymerizing hydrophilic vinyl nylon to a solution of a polyamide resin to make the polyamide resin water-soluble.

In particular, polyamide resins that are soluble in alcohol, such as N-methoxymethylated nylon called type 8 nylon, copolymerized nylon, etc., may be used, but 0.1 part or more of a hydrophilic vinyl monomer is added to 1 part of polyamide resin, and a polymerization catalyst is added. It is then heated and stirred to polymerize, resulting in longevity. The polyamide resin used in the present invention is an alcohol-soluble polyamide resin, such as N-ethoxymethylated nylon, N-ethoxymethylated nylon,
ON-flucoxymethylated nylon such as N-butoxymethylated nylon, copolymerized nylon, alcohol/calcium chloride OJ-soluble polyamide resin, such as nylon 6
, nylon 66, etc. Hydrophilic vinyl monomers include acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate,
Examples include polyethylene glycol monomethacrylate, itaconic acid, acrylamide, N-methylol acrylamide, and mixtures thereof.

As the polymerization catalyst, those commonly used for carrying out radical polymerization reactions, such as azobisisobutyronitrile and benzoyl peroxide, may be used. The water sieving nylon is
Since carboxyl groups, hydroxyl groups, etc. are hydrogenated, it also reacts with epoxy groups.

Specifically, for example, it is represented by the following chemical formula.

This may be further grafted with acrylic acid, acrylamide, etc. to add a carboxyl group to make it water-soluble. The above-mentioned cresol novolac type epoxy compound is added to this, or water-soluble nylon (B1/cresol novolac type epoxy compound
)/contains too/1o-1tl (J/80).

In particular, it is preferable to mix them at a ratio of 100/10 to 10150 (it ratio). If (B)/(4) is out of the above range, the adhesion of water-soluble nitrogen to the polyester fibers will be poor, resulting in decreased carburability or hardness, resulting in decreased fatigue resistance. The total solid content concentration including water-soluble nylon + Bl and cresol novolak type epoxy compound (4) is 1 to 3 (I wt %), preferably 3 to 20 wt %, based on the weight of the fiber. If the concentration is too low, Adhesiveness decreases and if the concentration is too high, it becomes hard and fatigue resistance decreases.

Polyepoxide compound (C
1 is a compound containing at least two or more epoxy groups in one molecule, 0.21/11 or more per 10011 of the compound, and is a compound containing polyhydric alcohols such as ethylene glycol, glycerol, sorbitol, pentaerythritol, and polyethylene glycol. Reaction products with halogen-containing epoxides such as epichlorohydrin, resorcinol,
Reaction products of polyhydric phenols such as 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. Polyepoxide compound obtained by oxidation, beaten 3.4-epoxycyclohexene epoxide,
3.4-Epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate.

Bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate and the like can be mentioned. 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 used as an emulsion.To make an emulsion or a solution, for example, such a polyepoxide compound may be dissolved as it is or if necessary in a small amount of a solvent, and may be mixed with a known emulsifier, such as , sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, rum salt, nonylphenol ethylene oxide adduct, etc. to emulsify or dissolve.

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 the blocking component is liberated by heating to produce an active polyincyanate compound. It is something that forces you to do something. Examples of the polyisocyanate compound include polyinocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylisocyanate, and triphenylmethane triisocyanate, or these polyisocyanates with two active hydrogen atoms. A terminal insyanate group-containing compound obtained by reacting a compound having at least 1 incyanate group, such as trimethylolpropane, pentaerythritol, etc., at a molar ratio of incyanate group (-Neo) to human hydroxyl group (-OH) exceeding 1. Examples include polyalkylene glycol adduct polyisocyanate.

In particular, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenylisocyanate are preferred because they exhibit excellent performance.

Examples of blocking agents include phenols such as phenol, thiophenol, cresol, and resorcinol, aromatic secondary amines such as diphenylamine and xylidine, phthalic acid imides, lactams such as caprolactam and valerolactam, and acetoxime. , methyl ethyl ketone oxime, cyclohexane oxime and other oximes, and acidic sodium sulfite.

Rubber latex (g) used in the first treatment agent of the present invention
For example, natural rubber latex, styrene,
Butadiene copolymer latex, vinylpyridine
There are styrene butadiene terpolymer latex, nitrile rubber latex, chloroprene rubber latex, etc., and these can be used alone or in combination. Among these, vinylpyridine-styrene-butadiene terpolymer latex shows excellent performance when used alone or when used at 1/241 or more.

The first treatment agent contains the above-mentioned polyepoxide compound (0), blocked polyincyanate compound (El) and warped rubber latex (0), (2), and (2) (compared to the blend type of each component)/ [S) Jukan)] is 0.05-0.9, (
B) / ((o) + (DJ) is preferably used in a range of 0.5 to 15.Special K (01/
[(0)+(9)] is 0.1~0.5, trunk 1/((0
It is preferable to mix so that 1+ (DJ) is in the range of 1 to 10. Here (01/ ((ol+(2))
If it is out of the above range, the adhesion rate of rubber to polyester fibers tends to be poor, and the adhesion tends to decrease.
If B1/((01+(DJ)) is smaller than the above range, the treated polyester fiber will become hard, leading to a decrease in fatigue resistance; come.

The total solid content including the polyexit compound (2) and the blocked polyinsyanate compound (Di rubber latex (2)) is 1 to 30 wt%, preferably 3 to 20 wt%, based on the fiber mold plate. and use it. 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 the above range is exceeded, the adhesiveness tends to decrease slightly.

The second treatment agent of the present invention is a composition containing rubber latex in resorcinol/formalin, and the resorcinol/formalin rubber latex used here is usually called RFL, which has a molar ratio of resorcinol and formaldehyde. The ratio is 0.1 to 1:8, preferably 1:0.
．． It is used in a range of 5 to 1:5, more preferably 1:1 to 1:4.

Examples of the rubber latex include natural rubber latex, styrene getadiene copolymer latex, vinylpyridine styrene getadiene terpolymer latex, nitrile rubber latex, chloroprene rubber latex, etc., and these may be used alone or in combination. Among these, vinylpyridine/styrene bone butadiene 9 terpolymer latex shows excellent performance when used alone or when used in an amount of 1/2 or more.

The blending ratio of resorcinol or formalin and rubber latex depends on the addition ratio of the ethylene urea compound (F) and talesol novolak type epoxy compound (described later), but the solid content ratio is preferably 1=1 to 1:15. is 1:3~
It is desirable that it be in the range H of l:12.

If the ratio of rubber latex is too small, the treated polyester fiber material will become hard and the fatigue resistance will deteriorate.On the other hand, if it is too large, the required fitting force and rubber adhesion rate will not be obtained.

The mixing ratio of the ethylene urea compound (F) and the cresol novolac type epoxy compound (4) is 40/60 to 80/
20 (mold plate ratio) is preferable, and the mixture has a ratio of 0.5 to 30 wl, preferably 1.0 to 20 wl, relative to the above RFL.
t% added.

If the amount of the mixture added is too small, good fitting force and rubber adhesion rate cannot be obtained. On the other hand, if the amount added is too large, the viscosity of the processing agent will increase significantly and the processing operation of the fiber material will become inconvenient. Moreover, when the fitting force and the rubber adhesion rate reach a saturation value, the amount of the mixture added will not be effective and the cost will only increase, and the fiber material after treatment will become stiff and hard. The disadvantage is that the strength is reduced.

The ethylene draft compound added to the second treatment agent is represented by the following general formula (F).

socyanate, hexamethylene diisocyanate, inhorn diisocyanate, tolylene diisocyanate,
Examples include meta-xylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, and triphenyl reaction products. In particular, aromatic ethylene urea compounds such as diphenylmethane diethylene urea give good results. In the present invention, ethylene urea compound (1') and cresol novolac type epoxy compound (Gl) have a mutual catalytic effect, and the ethylene urea compound is surrounded by an ethyleneimine wall, and in the talesol novolac type epoxy compound, the epoxy ring opens and reacts, resulting in adhesive properties. At the same time, it increases the cohesive force of the conventional agent itself, and as a result, forms a strong chemical bond with the amines generated in the rubber, thereby preventing adhesion and deterioration.Furthermore, it is applied as the first treatment agent. Due to the synergistic effect with the heat resistance of the T1y resin, dependence deterioration is suppressed to a minimum, thereby exhibiting good heat-resistant adhesive properties.

The above-mentioned second processing agent is usually adjusted to contain a solid content of 10 to 25% by weight.

K for attaching the first treatment agent and the second treatment agent to the polyester fiber material may be applied by any method such as contact with a roller, application by spraying from a nozzle, or immersion in a solution. The solid separation If wrinkles for polyester fibers is 0.1 to 1 as the first treatment agent composition.
It is suitable that the amount of the second treating agent composition is 0% by weight, preferably 0.5 to 5% by weight, and 0.5 to 10% by weight, preferably 1 to 5% by weight. In order to control the amount of solid content attached to the fibers, squeezing is performed using a pressure roller.

Means such as scraping off with a souffle bar, blowing off with air, and beating with a suction beater may also be used.

In the present invention, after the polyester fibers are treated with the first treatment agent, they are dried and heat treated at a temperature of 50°C or higher, preferably 10°C or more lower than the melting point of the polyester fibers, preferably 220 to 260°C, and then subjected to the second treatment. Treated with agent, 12
Drying and heat treatment are performed at a temperature of 0°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, adhesion with rubber will be insufficient, while if the temperature is too high, the polyester fibers will melt or fuse, or the strength will significantly decrease, making it impossible to put it to practical use.

<Effects of the invention> Compared to the conventional method, the fibers treated by the method of the present invention have
Heat-resistant adhesion is improved, and durability in terms of peel strength and pull-out strength is improved without impairing moldability with rubber.

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

In the examples, the heat resistance in rubber, cord peeling and fitting strength, T adhesion strength, and ply peeling force are values determined 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, the tensile strength at break was determined at a speed of 200 m/-, and the retention rate was determined by comparing it with the initial strength.

Cord Peel Adhesion Strength〉 Indicates the adhesive strength between the treated cord and rubber. Five cords were buried near the surface layer of the rubber sheet and heated at 150℃ under pressure.
It was vulcanized for 30 minutes and then cured.

〉T Adhesive Strength〉 Indicates the adhesive strength between the processing hood and rubber. The cord was embedded in a rubber block and heated at 150℃ for 30 minutes under pressure.
Vulcanize for 20 minutes, then remove the cord from the rubber block for 200cm/
Pull it out at the speed of Maro, and the force required to pull it out is kg/<I
It is indicated by N.

<Peeling force between plies> This shows the adhesion strength with treated coat F.

Two plies of treated cords were embedded in rubber as cross-plies (cord density: 27 cords/inch) at a 90 degree angle and cured at 150°C for 30 minutes.
The force required for peeling at a tensile speed of 0 H/m is kf/
It is displayed in 1 nch.

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

Examples 1 to 6 Comparative Examples 1 to 7 ■ Torezin F8-soo (manufactured by Teikoku Kagaku Rigyo ■; Acrylic 7 midograft compound of N-methoxymethylated nylon with degree of methoxymethylation of 30%; graft rate 25%) 20
'% bath solution 10 (1'), dissolve gON-1299 (Ciba Geigy ■; epoxy compound of phenol-formalin resin condensate) 8I in toluene in advance, Neocol F? < Dai-Kogyo Seiyaku (manufactured by ■; dioctyl sulfosuccinate sodium salt) (1,1 lI and 0.69 methyl cellulose were added and dissolved in 28 l of water. Added and dispersed with stirring, and mixed.
Add to 5UII with stirring and dissolve uniformly to obtain a pretreatment agent.

As a surfactant, Neocol 08W-30 (IN4-Kogyo! lll Mulberry f
Add 4I (manufactured by IIJ; 30% aqueous solution of dioctyl sulfosuccinate sodium salt) and dissolve uniformly. Add this to 5 osy of water while stirring, and
11 is uniformly dissolved in water. Next...Iren ■up
(Made by 7"z-pon; 4.4-diphenylmethane diisocyanate 7-propylene polymer) 14g1 neo=
- Dispersion obtained by mixing 42N of Ru ■8W-304JF water in Pall Mill for 24 hours and = Tpol ■2
518GL (manufactured by Nippon Zeon ■; 40 weight-water emulsion of vinylpyridine/styrene-butadiene terpolymer) 1
Add 254F and mix evenly. The obtained mixed liquid is added to the first
Use as a processing agent.

In addition, in the aqueous solution obtained by adding 101, 28 thioacid aqueous solution 3° OIi to 260I water and stirring well, resorcin-formalin initial condensation # (40 thiacetone solution) 60I reacted with an acidic catalyst was added.
Add and stir under sufficient pressure to disperse. Next = Tupol■
2518GL (manufactured by Nippon Zeon ■, vinylpyridine-styrene-getadiene-terpolymer latex 40% water emulsion) 240.9 and Nirapol L, -112 (manufactured by Nippon Zeon@, 40% styrene-butadiene copolymer)
Water emulsion) 100.9 is diluted with water 200II. The resorcinol/formalin precondensed solution is slowly stirred into this diluted solution, and 20 JF of formalin (37% aqueous solution) is added and mixed uniformly.

Next, add 1 part of diphenylmethane diethylene urea to this mixture.
411, Neo-Ru ■8W-305,9, and 36 g of water were stirred and mixed in a ball mill for 24 hours, and an aqueous dispersion obtained was added and mixed. Next, FiON1299 (manufactured by Chipa Geigy ■, an epoxy compound made of phenol/formalin resin cotton metal) 7.2N was dissolved in toluene in advance, and Neo-R ■P (manufactured by Daiichi Kogyo Seiyaku ■, dioctyl sulfosuccinate) was dissolved in toluene in advance. Sodium salt) 0.1 g and 0.61 g of methyl chloride were added and dissolved in water28
The dispersion was added to JF with stirring and mixed, and the resulting liquid mixture was used as a second treatment agent.

[η) = 0.89 polyethylene terephthalate was melt-spun and stretched according to a conventional method to obtain 1500 denier/1
A multifilament of 92 filaments was obtained.

Next, the multifilament 2 wood is 40 x 40'l'
A cord of 3000 denier/384 filament was obtained by twisting the yarn at /10 degrees.

These =- cords were immersed in the pretreatment agent using an MP Treater ■ treatment machine (0 person Suller 11 tire cord treatment machine), and then dried and cured at 130°C for 3 minutes.

The pretreatment agent treatment can also be carried out at the time of the back yarn. The amount of pretreatment agent deposited was 3.5 wt%.

Subsequently, after being immersed in the first treatment agent, it is dried at 150°C for 2 minutes, and then heat-treated at 230°C for 1 minute.

Next, after being immersed in the second treatment agent, it is dried at 150°C for 2 minutes, and then heat-treated at 230°C for 1 minute. The treated polyester tire cord has a solid content of the first treatment agent of 2.
The solid content of the second treatment agent was adhered to L5 wt.

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.
Vulcanization was carried out for 0 minutes (initial value) and at 170° C. for 90 minutes (heat resistance i).

As shown in Table 1 for the above experiment, the pretreatment agent (N-methoxymethylated nylon acrylamide graft compound)
The weight ratio of and Talesol novolac type epoxy compound (a) was changed variously, and the second treatment agent ethylene urea compound ←゛) and Talesol novolac type epoxy compound @(
The experiment was repeated with various changes in its weight ratio.

The experimental results are shown in Table 1.

Initial value: Value after embedding the treated cord in unvulcanized rubber with a carcass composition mainly composed of natural rubber and vulcanizing it at 150°C for 30 minutes.

Claims (1)

[Claims] (1) Linear aromatic polyester fiber is expressed by the following general formula (A)
treated with a pretreatment agent containing a cresol novolac type epoxy compound represented by: After treatment with a processing agent, the ethylene urea compound represented by the following general formula (F) and the above-mentioned cresol novolac type epoxy compound (A) are added to resorcinol, formalin, and rubber latex (RFL) (F)/(A)=
A method for treating polyester fibers, comprising treating with a second treating agent added in a weight ratio of 40/60 to 80/20. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(A) [Here, R' is -O■CH_2)_k-Cl, -O■C
H_2■_lOH or [O■CH_2)_m]_m_
'OH, R'' is either 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, a+b ≦6.] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(F) [Here, R is an aromatic or aliphatic hydrocarbon residue, and n is 0, 1 or 2. When n=0, the terminal group is hydrogen.]