DE2334921A1 - ANTISTATIC POLYAMIDE FIBERS WITH A REDUCED PROBLEM TO BUBBLE - Google Patents

Description

ALLIED CHEMICAL CORPORATION, Morristown, N.J. ( UNITED STATES.) Ad / Win. Morristown, N.J.

Antistatic polyamide fibers with a reduced tendency to pimple.

This invention relates to a method for melt spinning a filament structure from a synthetic polyamide polymer. In particular, it relates to a method for making an improved antistatic thread, Yarn or the like by melt-spinning a synthetic linear fiber-forming polyamide.

It has already been proposed to increase the usability of synthetic fibers and their properties, in particular to improve their antistatic properties, by using a high molecular weight polyalkylene ether is incorporated into the polymer. U.S. Patent 3,475,898 specifically describes the use of poly (ethylene propylene) ether glycols for this purpose. It is also described in U.S. Patent 3,657,386 that certain Propylene oxide / ethylene oxide copolymers based on ethylene diamine are particularly suitable in the production an antistatic polyamide fiber.

In the case of polyamide fibers, the propylene oxide / ethylene oxide copolymers on the basis of ethylenediamine, problems have arisen when spinning from the melt because of

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the paser often has pimples. The term "knobs" is used in the usual sense and means herein thickened sections of the thread which are no more than several thread diameters in length. Pimples can be formed by a foreign, non-orientable substance, which hinders normal fiber elongation over a short area and leads to thickening. Foreign bodies that are likely to contribute to the formation of tufts, are carbonilolerte polymers _# from the extruder and the spinning nozzle as well as gels formed in the polymer. The gels are considered to be the main cause, ie the pimples are probably caused by a non-orientable gel made of cross-linked polymer. Thermal degradation of the polymer can be an important factor in the formation of the pimples. The reactions that occur during the thermal degradation of polyamides containing polyalkylene ethers have not yet been clarified. It is probable that a decomposition product is formed through thermal degradation, whereby crosslinks are formed between amide groups and adjacent polymer chains. The decomposition reaction proceeds slowly, and finally a three-dimensional molecular network is built up, which can be called polymer gel and which finally reaches a stage in which it forms an infusible coating on the reactor walls and other devices.

A serious difficulty involved in the formation of this polymer gel on the inner walls is that pieces break off from time to time, which are in the flowing polymer stream and thus cause damage to the spinning device.

The greatest difficulty, however, is caused by polymer gel, which has indeed reached the three-dimensional structure but not yet the infusible stage. This kind

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of polymer gel is easily carried along by the polymer stream. In the molten or at least softened state, it passes through the pump and even the filter medium and shows up afterwards either as a non-uniformity or as a viscosity fluctuation in the spun thread. At the later Cold drawing of these threads can cause these faults to break the threads, whereby either the whole thread tears off or knobs are formed, which are assessed as a quality defect in the end product.

According to the invention, the above-mentioned difficulties are avoided by preventing gel formation in the molten Polyamide decreased. Furthermore, according to the invention, an enrichment of the polymer gel a ^ the reactor walls in the pump and in the filter medium when spinning in the melt of the polyamide avoided. It also gets the evenness and quality of the filaments or fibers formed from the molten polymer improved and the pimple formation in the Threads decreased. Other objects will be apparent from the description and claims.

The present invention relates to an improvement of the method for production of antistatic polyamide fibers, comprising a fiber-forming Polyamidpolymerisat that 1-12 wt.% Of an antistatic compound of the formula

CH ₅ CH ₃

H (OCH ₂ CH ₂ ) _g (OCHCH ₂ ) _c ^ (CH ₂ CHO) _a (CHgCH ₂ 0) _e H.

CH ₅

H (OCH ₂ CH ₂ ) _h (OCHCH ₂ ) ₍ f ^ (CH ₂ CHO) ₁ , (CH ₂ CH ₂ '

contains.

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in which «

a, b, c, d, e, f, g and h are each an integer, the sum of a, b, c and d is between 8 and 850 and the sum of e, f, g and h is between 8 and 1,000, and wherein the molecular weight of the antistatic compound is 4,000 to 5,000 and the ethylene oxide type part accounts for 20 to 80% of the molecular weight of the compound,

by extruding the molten polymer through an opening into a cooling medium and then stretching it of the filaments formed, which is characterized in that at least 0.1 wt. ^ preferably 0.5 to 8 wt. ^, based on the weight of the antistatic compound, a phenolic compound of the formula

(lower) alkyl

(CH ₂ ) _x -CO- (C _y H _2y ) -H (lower) alkyl

χ has a value from 1 to 6 and y has a value from 6 to 350

or a compound of the formula

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where R

(lower) alkyl HO

(lower) alkyl

It

(CH ₂ ^ ₁ -CO- (CH ₂ ) _yl .

a value from 1 to 6 and a value from 1 to

y have ¹ solves.

If the term "alkyl" is replaced by the term "(lower)" is defined in more detail, one means a branched or straight chain Hydrocarbons with 1 to about 6 carbon atoms,

It is preferred to use a phenolic compound together with at least 0.1 wt. #, based on the weight of the antistatic additive, a sulfur compound of the formula

C _n H _2n ) -COOR "

(C _n H _2n J-COOR "

where R "

an alkyl radical containing 8 to 10 carbon atoms

is and

1 to j5 means.

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As already described above, the present invention is an improvement over US Pat. No. 3,657,386, which relates to an antistatic polyamide fiber containing tetroi compounds which are propylene oxide / ethylene oxide copolymers based on ethylene diamine. The tetrol compounds to be used as an antistatic additive can be prepared as described in US Pat. No. 2,979,528.

The invention also relates to antistatic Polyamide fibers containing 1 to 12 wt. # Of an antistatic compound of the formula

H (0CH ₂ CH ₂ ) _£ (0CHCH ₂ )

H (OCH ₂ CH ₂ ) _h (OCHCH ₂

where a, b, c, d, e, f, g and h are an integer and the sum of a, b, c and d is between 8 and 850 and the sum of e, f, g and h is between and 1000 and the molecular weight of which is 4000 to 50,000, the ethylene oxide component making up 20 to 80 % of the molecular weight of the compound,

characterized in that the fibers are at least 0.1 wt. based on the weight of the antistatic compound of a phenolic compound of the formula

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(lower) alkyl

11

(CH ₂ ) _x -C-O- (C _y H _2y ) -H

(lower) alkyl

χ has a value from 1 to 6 and y has a value from 6 to 30

or a compound of the formula.

R .R ^c

wherein. R.

(lower) alkyl

ti

. '(lower) alkyl

with x ¹ and y ^f = 1 to 6 _t included «

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The alkylated phenol compounds to be used according to the invention are known compounds and some of them are already commercially available. One can easily alkylate the phenols with a Perform a variety of catalysts and alkylating agents (see Price, organic Reactions, III, 58 (19 ^ 6)). The production of 2,6-dialkylphenols by direct Alkylation is relatively difficult. However, such a method is in the "Journal of Organic Chemistry", 21 712 (1956). Reference is also made to US patents 3 285 855 and 3 330 859 pointed out.

The sulfur compounds according to the invention can by the method in Chemical Abstracts, 64, 3562c or according to the U.S. Patent No. 2,762,836.

The antistatic fiber of the present invention can also conventional fiber additives, such as antioxidants, Stabilizers, matting agents, dyeing auxiliaries and dyes.

The antistatic additives in the examples are Tetrol compounds of the general formula

H (0CH ₂ CH ₂ ) _g (0CHCH ₂ )

H (OCH ₂ CH ₂ ) _h (OCHCH ₂ )

CH,

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a, b, c, d, e, f, g and h each represent an integer and the sum of a, b, c. and d between 8 and 850 and the sum of e, f, g and h between 8 and 1000 lies.

Suitable tetroi compounds are commercially available under the trademark "Tetronic" (BASF / Wyandotte); the trademark Tetronic comprises a series of poly (oxyethylene) · poly-ioxypropylene / block copolymers with molecular weights between 1,650 and over 26,000.

This series differs in the length of the poly (oxy » ethylene) and poly (oxypropylene) Ke "cten. A 3- and The 4-digit key number indicates the molecular composition. When 4 digits are used, they show first two the average molecular weight of the hydrophobic polyoxypropylene branches on the alkylenediamine. If only 3 digits are used, only the first digit is used for this purpose. The last digit everyone Key number represents the content of hydrophilic poly (oxyethylene) units rounded up in percent by weight to the nearest 10 #. The tetra oil compounds in the examples are described in this way.

The following examples serve to explain the subject matter of the invention in more detail, but without restricting it.

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Example 1: * "

A glass reaction vessel equipped with a heater and a stirrer was charged with a mixture of 1520 g of ε-caprolactam and 80 g of aminocaproic acid. The mixture was then purged with nitrogen and heated to 255 ° C. for one hour under atmospheric pressure with simultaneous stirring. Heating and stirring were continued under a nitrogen blanket for an additional 4 hours to complete the polymerization reaction. During the last 30 minutes of the polymerization, 2.7 g of tetra / ^ methylene 3- (3'-5 ^l -di-tert-butyl-4 ^l hydroxyphenyl) propionate-7-methane and 90 ε of the antistatic tetroi compound "Tetronic 1508" (molecular weight 27 with an ethylene oxide content which is 80 % of the molecular weight) was added to the polycaproamide, and stirring was continued for the purpose of thorough mixing. The tetra ^ methylene 3- (3 ', 5'-di -tert-butyl-V- hydroxyphenyl) propionate 7-methane is commercially available under the trademark "Irganox 1010" and has the formula

0 dd

<i

OH

A low pressure was then applied with a supply of nitrogen maintained in the reaction vessel and the polymer is extruded in the form of a tape from the reaction vessel. The polymer tape was cooled, pelletized, washed and then dried. It became a white, solid polymer

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obtained with a relative viscosity of about 55 to 6o. The viscosity was measured at a concentration of 11 g in 100 ml of 90 #iger formic acid at 25 ⁰ C. (ASTMD-789-62T).

The polycaproamide pellets containing the antistatic agent and the phenol compound were at about Melted 285 ° C and then extruded through an open 16-hole nozzle under a pressure of 1,500 psig. The holes the nozzle was 0.0 ^ 6 cm (0.014 inch) in diameter, so that a fiber with a titer of 250 den was obtained. The fiber was fed at a speed of J500 m / min added and drawn to about 3.5 times the extruded length, so that a yarn with a linear density of 70 that was created.

For the sake of simplicity, this yarn will be called Yarn A in this description. A control yarn containing the antistatic but no other additives was made using the same procedure described above. This GarYi is called Yarn B in this description. .

Yarn A and yarn B are twisted into a simple conventional one Fabric processed.

The tissues became test specimens measuring 7.6 × 22.86 cm cut up. These fabric samples were tested for their antistatic properties according to the general method in TECHNICAL MANUAL OF THE AMERICAN ASSOCIATION OF TEXTILE CHEMISTS AND COLORISTS, (I969 Edition), £ 4, 206-207, described method. This test method is called "Electrostatic Clinging of Fabrics: Fabric-to-Metal Test "and is under the number A.A.T.C.C." I5-I969, registered. This test method is referred to below as the tissue / metal adhesion test.

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Yarn A as well as Yarn B both showed excellent antistatic properties in the test, e.g. the average time it took tissue samples to completely detach themselves from the metal, approximately 150 seconds after 25 washes. In yarn A and yarn B also checked the number of nubs per 0.45359 kg, as shown in example 2.

Example 2 t

This example describes the method used herein for the localization, identification and calculation of the knobs per 0.1359 kg in those produced according to Example 1 Yarns A and B. In this method, a nub is referred to as a thickened section in a thread which is no more than several thread diameters in length. This method can be used with monofilament or Multifilament yarns are used, but it is not can be used with most crimped yarns.

After the method described, the yarn was with a Titer of 70 denier drawn directly from the coil by means of a suction device and through an opening of known Size, namely 0.076 mm wide, led.

When using a ceramic wiper, which is well known in the art, such a defined opening can easily be obtained. When a nub appears, the yarn is no longer guided through the opening. The threads are separated and the reason why the thread is not transported further is recognized as a nub or as the twisted end of a broken thread. In order to achieve representative results, about 75 g of yarn are passed through the opening and the number of knobs is counted. Table 1 shows the results of the test on yarn A and yarn B.

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60

Table I.

Determination of the number of nubs per 0.45359 kg (lpound)

Yarn sample pimple count , r> nn _r 4f> ^ 9 kg of yarn.

Thread A 1.5 x 10 " ⁵

Yarn B 16.Ox 10- ⁵

It is noteworthy that the antistatic proportioning rate to the polyamide resulted in a number of knots of 16.0 χ 10- ⁵ per pound of yarn, which is much higher than that of normal polyamide fiber. However, the addition of an antistatic together with the phenolic compound reduced the number of nubs to 1.5 x 10 ⁵ nubs per 0.45359 kg of yarn.

Example ^;

The procedure of Example 1 (yarn A) was repeated, but 90 g of the flat antistatic described in Example 1 were added together with 2.7 g of octadecyl-3- (3 '# 5'-di-tert-butyl-4'-hydroxyphenyl) - propicnat added to the polycaproamide. The resulting Paser was bright yellow and had 1.0 χ 10 ⁵ stems per 0.45359 kg yarn. The octadecyl-> (3 ¹ , 5 ^f -di-tert-butyl-4 ^f -hydroxyphenyl) propionate is available commercially under the trademark "Iranox 1076" and corresponds to the formula

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Example 4;

The procedure of Example 1 (Yarn A) was repeated, except that 90 g of the antistatic described in Example 1 were used together with 1.25 g of tetra / methylene 3- (3 '* 5'-di-t butyl-4'-hydroxyphenyl) propionate / methane and 1.35 g Distearyl thiodipropionate is used. The fiber obtained was light yellow and had 1.5 x ICr Pimples per 0.45359 kg of yarn.

Example 5 '.

The procedure described in Example 1 (yarn A) was repeated, but 90 g of the antistatic "Tetronic 1504" were used together with 2.7 g of tetra / methylene 3- (3'-di-t-butyl-4'-hydroxyphenyl) propionate-7-methane used. ("Tetronic 1504" has a molecular weight of about 12,500 and the ethylene oxide content is about 40 % of the molecular weight). The fiber obtained was light yellow and had 1.5 × ICr knobs per 0.45359 kg of yarn.

Example 6:

The procedure described in Example 1 (yarn A) was repeated, but 90 g of the antistatic from Example 5 were used together with 2.7 g of octadecyl-3- (3 ', 5'-diisopropyl-4'-hydroxyphenyl) propionate.

The fiber obtained was light yellow and had 1.5 x ICr Pimples per 0.45359 kg of yarn.

Example 7:

The procedure described in Example 1 (Yarn A) was repeated, except that 90 g of the antistatic was obtained from . Example 5 together with 1.35 g of dream ethylene 3- (J ', 5'-aged, -butyl -4' -hydroxyphenyl propionate methylene and 1.35 g

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Distearyl thiodipropionate is used.

The fiber obtained was light yellow and had 1.4 χ ICr Pimples per 0.45359 kg of yarn.

Example 8:

The procedure described in Example 1 (Yarn A) was repeated, but the additions were already made added to the caprolactam. The fiber obtained was light yellow and had 1.5 χ lcr pimples per 0.45359 kg Yarn on.

Example 9;

The procedure described in Example 1 (yarn Λ) was repeated, but the antistatic was added to the caprolactam without the addition of a phenolic compound, The antistatic fiber obtained was deep yellow and had a high nub count of 16.0 × 10 ^ nubs per 0.45359 kg Yarn on.

Example 10:

The procedure described in Example 1 (yarn A) was repeated, but 90 g of the antistatic from Example 1 were used together with 1.35 g of tetra ^ methylene-3- (3 ' β 5'-di-tert-butyl-4'- hydroxyphenyl) propionate 7 methane and 1.35 g dilauryl thiodipropionate.

The fiber obtained was light yellow and had 1.8 χ ΙΟ · ' Pimples per 0.45359 kg of yarn.

It can be seen from this that the dilauryl thiodipropionate is also an effective thioester which is used together with the phenol compound according to the invention can be,

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Example 11; The procedure described in Example 1 (Yarn A) "was repeated, but 90 g of the antistatic from Example 1 were combined with 2.7 g of tetra / methylene 3- (3 '# 5'-di-isopropyl-4'-hydroxyphenyl) propionate-methane. used.

The fiber obtained was light yellow and had 1.8 χ IQr knobs per 0.45359 kg of yarn.

Example 12:

The procedure described in Example 1 (yarn A) was repeated, but 90 g of the antistatic from Example 1 were used together with 2.7 g of octadecyl-J-CJ ¹ ^ ¹ -di-isopropyl-4'-hydroxyphenyl) propionate. The paser obtained was light yellow and had 1.4 × 10 ^ pimples per 0.45559 kg of yarn.

Example 13; The process described in Example 1 (yarn A) was repeated, but 90 g of the antistatic from Example 1 were added together with 0.9 g of tetra / methylene ^ -Ο ', δ ¹ -di-tert-butyl-4'-hydroxyphenyl) propionate7 -methane used. The paser obtained was light yellow and had 1.9: c 10 ^ pimples per 0.45359 kg of yarn.

Example 14:

The procedure described in Example 1 (yarn A) was repeated, but 90 g of the antistatic from Example 1 together with 1.8 g of tetra / methylene 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate7 -methane used. The Paser obtained was bright yellow and had 1.7 χ 10 ⁵ stems per 0.45359 kg yarn.

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Example 15:

The procedure described in Example 1 (yarn A) was repeated, but 90 g of the antistatic from Example 1 together with 3.6 g of tetra-ethylene 3- (3 ', 5'-Ui- / tert, -butyl-4. -Hydroxyphenyl ) ^{Propionat7 r} -methane is used. The fiber obtained was light yellow and had 1.3 χ ICr per 0.45359 kg of yarn.

Example 16;

The procedure described in Example 1 (yarn A) was repeated, but 90 g of the antistatic from Example 1 were added together with 4.5 g of tetra / ethylene 3- (3 ', 5 ^f -dltert.-butyl-4'-hydroxyphenyl) propionate7- methane used. The paser obtained was light yellow and had 1.3 × 10 ^ per 0.45359 kg of yarn.

Example 17 t

The procedure described in Example 1 (yarn A) was repeated, but 60 g of the antistatic from Example 1 were used together with 1.8 g of tetra-ethylene 3- (3 ** 5 * -di-tert-butyl-4 ^f -hydroxyphenyl ) propionate7-methane. The resulting fiber was bright yellow and had 1.3 χ ¹ O ^ stems per 0.45359 kg yarn.

Example 18:

The procedure described in Example 1 (yarn A) was repeated. However, 44 g of the antistatic from Example 1 were used together with 1.32 g of tetra ^ / methylene 3- (3 ', 5'-di-tert-butyl-4 ^f -hydroxyphenyl) propionate-7-methane. The fiber obtained was light yellow and had 1.1 × 10 ^ nubs per 0.45359 kg of yarn.

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Example 19;

The procedure described in Example 1 (yarn A) was repeated, but J> 0 g of the antistatic from Example 1 together with 0.9 g of tetra-inethylene 3- (3 '^' - ditert.-butyl ^ '- hydroxyphenyl) propionate7- methane used. The fiber obtained was light yellow and had 0.8 × 10 × ^ knobs per 0.45359 kg of yarn.

Example 20:

^{Polycaproamide pellets containing the antistatic agent and tetra methylene "3} J- (j5 ', 5' -di-tert-butyl-4 '-hydroxyphenyl) propionate / zniethanum described in Example 1 were prepared by the method of Example 1 The polycaproamide pellets were ^{melted at 285 °} C. and under a pressure

of 105 kg / cm from the melt through a 70-hole spinning nozzle. The single hole diameter of the spinneret was 0.045 cm, and it became a multifilament with a Received titers of -4500 den. The multifllament was at withdrawn at a speed of J500 m / min and stretched to about 4 times the extruded length. The titer of the yarn thus obtained was 1125 dan.

The yarns were textured by means of a steam jet nozzle and two yarn ends were twisted around each other. The yarns were processed into a carpet with a smooth loop fabric. The number of stitches was 6.5 and the pile height 9-10/32 inches. The carpet was dyed blind and provided with a latex backing. The static charge on the carpet was tested according to the "shuffle test" by measuring the build-up of electrostatic voltage on a person who walked the carpet with short scraping steps. The carpet was conditioned at 21.6 ⁰ C and 20% relative humidity. The resulting voltage was 4.8 KV. .

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The pimple counting procedure of Example 2 was also used to determine the pimple of the untextured Yarn. In this test, the ceramic scraper had an opening of 0.15 mm. The untextured yarn showed 100 knobs per 0.45359 kg.

Example 21;

The procedure used in this example and the additives were analogous to example 1 (yarn A), however the polyamide was polymerized from Hexametnylenadiparaid.

A paser was produced and nubs as in Example 2 counted. The result was 1.5 χ 10 ^ studs per 0.45359 kg

In further experiments it has been found that the molecular weight of the antistatic must preferably be between about 4,000 and about 50,000, the ethylene oxide content being about 20 % to about 80 % of the molecular weight of the compound. Preferably, the antistatic fiber contains from about 2 % to about 8 % of the antistatic compound.

"Antistatic" fibers are to be understood as meaning fibers the fabric / tyletallhafttest and the "shuffle test" as described in U.S. Patent 3,657,386.

"Fiber" is to be understood as meaning multifilament yarns, monofilament yarns and all known physical forms of synthetic fibers. "Polyamide" is understood to mean the polymers which are produced by condensation of diemines with dibasic acids or by polymerization of lactams or amino acids, with synthetic resin characterized by the repeating group -CONH- being formed. "Ethylene oxide component" is to be understood as meaning the proportion of chemical molecules with the repeating grouping - (CH ₂ CH _{2 O) -.}

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It is aimed at the antistatic and the other additives to be distributed largely and evenly in polyamide.

The weight ratio of the phenolic compound to the sulfur compound is preferably between 0.25 and 4.0.

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Claims (8)

Claims 7334921 54 1. Process for the production of antistatic polyamide fibers, consisting of a fiber-forming Polyamide polymer containing 1 to 12 wt. # Of an antistatic compound of the formula H (OCH ₂ CH ₂ ) _g (OCHCH ₂ ) _Q (CH ₂ CHO) _a (CH ₂ CH ₃ O) _g H. H (OCH ₂ CH ₂ ) _h (OCHCH ₂ ) ₍ a, b, c, d, e, f, g, and h are each an integer and the sum of a, b, c .. and d between 8 and 850 and the sum of e, f, g and h is between 8 and 1000, by extruding the molten polymer through an opening into a cooling medium and then stretching it of the threads formed, characterized in that at least 0.1 wt. #, based on the weight of the antistatic compound, a phenolic compound of the formula: (lower) alkyl (lower) Al 48 - 21 - 309885/1283 wherein or one ■ r'ir.cjrx vert _from ] _ to 6 and cine :; '..' ert from 6 to JO has ίζ of the formula .R K ' where R wherein (lower) alkyl L s Λ (CH ₂ ) _x , -C-0- (CH ₂ ) _y r (lower) alkyl κ ' y ¹ a V.'ert from 1 to 6 and a value from 1 to 6 have solves. 2 The method according to claim 1, characterized in that 0.5 to 8 wt. *. based on the weight of the antistatic Compound, the phenolic compound can be dissolved in the extrudate prior to extrusion. Al 48 - 22 - 30988 5/1289 ? 33A92 3. The method according to claim 1 and 2, characterized in that at least 0.1 · G ^ew «#> based on the weight of the antistatic compound, a sulfur compound of the formula -COOR " R "is a C _q to C. _P alkyl radical and O JL .5 η means 1 to 3, dissolves in the extrudate prior to extrusion. 4. The method according to claim 3, characterized in that the weight ratio of the phenol compound to the sulfur compound Is 0.25 to 4.0. 3. The method according to claim 1 to 4, characterized in that the phenol compound tetra /, ~ methylene-3- (3 ^f »5 ¹ -altert.-butyl-4 ^! -Hydroxyphenyl) prop! Onate7-methane or octadecyl · 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate. 6. Antistatic polyamide fibers containing 1 to 12 wt. # Of an antistatic compound of the formula H (OCH ₂ CH ₂ ) _g (CCHCH ₂ ) _c H (OCH ₂ CH ₂ ) _h (OCHCH ₂ ) £ Al 48 - 23 - ^ 09835/1289 a, b, c, d, e, f, g and h are each an integer, and the sum of a, b, c and d is between 8 and 850 and the sum of e, f, g and h between 8 and 1000, and wherein the molecular weight of the antistatic compound is 4000 to 50,000 and the ethylene oxide content is 20 to 80 % of the molecular weight of the compound, characterized in that the fibers contain at least 0.1% by weight, based on the weight of the antistatic compound, of a phenolic compound of the formula (lower) alkyl (lower) alkyl x has a value from 1 to 6 and y has a value from 6 to 30 or a compound of the formula Al 48 - 24 - 0 9 B 8 b / 1 2 8 i) (lower) alkyl It (CH ₀ ^ ₁ -CO- (CH ₀ ) .- 2'y (lower) alkyl χ ^{1 has} a value from 1 to 6 and y ^{1 has} a value from 1 to contain. 7. polyamide fibers according to claim 6, characterized in that that they are 0.5 to 8 wt. # based on the weight of the antistatic Compound containing phenolic compound. 8. Polyamide fibers according to claim 6 and 7, characterized in that that they additionally at least 0.1 wt. based on the Weight of the antistatic connection, a S - '^ e free connection the formula -COOR " a Cg to C ^ alkyl radical and 1 to 3 means contain. - 25 - ^ 09885/1289 9 · polyamide fibers according to claim 8, characterized in that the ratio of the phenolic compound to Sulfur compound is between 0.25 and 4.0. 10 # polyamide fibers according to claim 6 to'9 # characterized in that the phenolic compound tetra / _ ~ methylene 3- (j5 ^f , 5 '-ditert. -Butyl-4' -hydroxyphenyl) propionate / ^r -methane or octadecy1-3- (3 ', 5 ^! -Di-tert-butyl-4'-hydroxyphenyl) propionate is. Al 48 - 26 - 309885/1289