US3801553A - Antistatic acrylic synthetic fibers and a process for the manufacture thereof - Google Patents

Abstract

AN ACRYLIC SYNTHETIC FIBER COMPRISING AT LEAST 70% BY WEIGHT ACRYLONITRILE AND FROM 2 TO 10% BY WEIGHT OF AT LEAST ONE POLYALKYLENE ETHER DERIVATIVE REPRESENTED BY THE FORMULA: R(-X-(CH2-CH(-R'')-O)N-H)M WHEREIN R IS A HYDROPHOBIC ORGANIC RADICAL OF FROM 6 TO 40 CARBON ATOMS DERIVED FROOM A COMPOUND HAVING A -OH OR A -COOH GROUP BY REMOVING SAID -OH OR SAID -COOH GROUP; R'' IS HYDROGEN OR METHYL; X IS O OR COO; N IS AN INTEGER LARGER THAN 2 AND M IS AN INTEGER OF FROM 1 TO 6. ALSO DISCLOSED IS A PROCESS FOR MAKING SUCH ACRYLIC SYNTHETIC FIBERS COMPRISING WET-SPINNING A POLYMER COMPRISING AT LEAST 70% ACRYLONITRILE INTO FILAMENTS, CONTACTING THE RESULTING FILAMENTS WITH THE ABOVE-IDENTIFIED POLYALKYLENE ETHER DERIVATIVE WITH AN AMOUNT OF THE DERIVATIVE, BASED ON THE DRY WEIGHT OF THE FIBERS, LARGER THAN THAT AMOUNT OF THE DERIVATIVE, BASED ON THE DRY WEIGHT OF THE FIBERS, WHICH REMAINS IN THE FIBERS AFTER THE FIBERS HAVE BEEN TREATED IN BOILING WATER FOR AT LEAST ONE HOURS. .

Description

April 2, 1974 RATE OF RESIDUE /o o m 4 0") 0o 5 HIROYUKI YAMAGUCHI ETAL 3,8 AN'I'ISTATIC ACRYLIC SYNTHETIC FIBERS AND A PROCESS FOR THE MANUFACTURE THEREOF Original Filed Dec. 22, 1969 SATURATION S -VALUE CURVE SATURATING PICK-UP l l I] I 5 IO I5 20 25 3O INITIAL DOSES United States Patent 3,801,553 ANTISTATIC ACRYLIC SYNTHETIC FIBERS AND A PROCESS FOR THE MANUFACTURE THEREOF Hiroyuki Yamaguchi, Kyoto, and Shigeyuki Komure,

lbaraki, Japan, assignors to Asahi Kasei Kogyo Kabushiki Kaisha, Osaka, Japan Continuation of abandoned application Ser. No. 887,215, Dec. 22, 1969. This application Oct. 5, 1971, Ser. No. 186,810

Claims priority, application Japan, Dec. 20, 1968, 43/ 93,139 Int. Cl. C08f 29/52, 45/00 US. Cl. 260-795 MU 13 Claims ABSTRACT OF THE DISCLOSURE An acrylic synthetic fiber comprising at least 70% by weight acrylonitrile and from 2 to by weight of at least one polyalkylene ether derivative represented by the formula:

wherein R is a hydrophobic organic radical of from 6 to 40 carbon atoms derived from a compound having a OH or a COOH group by removing said OH or said COOH group; R is hydrogen or methyl; X is O or COO; n is an integer larger than 2 and m is an integer of from 1 to 6. Also disclosed is a process for making such acrylic synthetic fibers comprising wet-spinning a polymer comprising at least 70% acrylonitrile into filaments, contacting the resulting filaments with the above-identified polyalkylene ether derivative with an amount of the derivative, based on the dry weight of the fibers, larger than that amount of the derivative, based on the dry weight of the fibers, which remains in the fibers after the fibers have been treated in boiling water for at least one hour.

CROSS-REFERENCE TO RELATED APPLICATION The present application is a continuation of US. application Ser. No. 887,215, filed Dec. 22, 1969, now abandoned, claiming priority from Dec. 20, 1968 based on Japanese patent application 'Ser. No. 93,139/1968.

This invention relates to an improved acrylic synthetic fiber having not only superior fiber characteristics, but also a highly favorable antistatic performance, and a process for the manufacture of such improved acrylic synthetic fibers.

While acrylic synthetic fibers possess favorable physical characteristics for use as textile materials and superior dyeing behavior, they show a strong tendency toward static characteristics.

Substantial troubles are therefore encountered during manufacture and use of acrylic synthetic fibers on account of the static charges accumulated therein by frictional contact between the fibers.

Various prior methods are known for the prevention of the accumulation of static charges in the acrylic manmade fibers. As an example, an antistatic agent selected 3,801,553 Patented Apr. 2, 1974 from the group of known surfactants is used for the treatment of such fibers for attaining the desired effect, but it has been experienced that the thus applied antistatic agent is frequently removed off even upon a single washing. Therefore, the antistatic efiect thus attained is not permanent. For obviating such a conventional drawback, it has also been proposed to use a certain kind of hydrophilic high molecular weight compound as the antistatic agent; however the results leave much to be desired with respect to the wash fastness of the fibers.

It is therefore the main object of the invention to provide a highly durable antistatic acrylic fiber which possesses superior physical characteristics per se.

It is now been found that if an acrylic fiber comprising an acrylic polymer contains in a suitable way at least 2 wt. percent of at least one member selected from the group consisting of polyalkylene ether derivatives represented by the general formula:

where R stands for a hydrophobic organic radical having 6-40 carbon atoms; R for a hydrogen or methyl group; and X for an oxygen atom or an ester bond, n being an integer larger than 2 and m also being an integer of 1-6,

the fiber has a superior antistatic performance, indeed, without any substantial loss of the originally owned fiber properties adapted for use as a textile fabric material.

The term acrylic polymer as used throughout the present specification and appended claims stands for an acrylonitrile polymer per se, or a copolymer comprising at least wt. percent of acrylonitrile and a monomer carrying another unsaturated radical or radicals.

Repesentative comonomers usable for the above purpose may be, among others, as follows: methacrylic acid; methyl acrylate; butyl acrylate; methyl methacrylate; ethyl methacrylate; butyl vinyl ether; acrylic acid ester; methacrylic acid ether; vinyl ether; vinyl acetate ester; styrene sulfonic acid; sodium styrene sulfonate; sodium allylsulfonate; sodium methallyl sulfonate. These examples are not intended to limit the present invention and other comonomers which are commonly used in the textile industry are also usable in the practice of the invention.

As was referred to hereinabove, the hydrophobic organic group of the polyalkylene ether derivatives should have 6-40 carbon atoms. With such polyalkylene ether derivatives having an organic radical with less than 6 carbon atoms, the desired effect would not be suificient for the purpose aimed at, and indeed, on account of insufiiciency of the hydrophobic performance of the organic radical.

When the number of carbon atoms exceeds 40, the molecule will become too large which results in unfavorable results. Such hydrophobic organic radicals (expressed by R) may be derived from compounds where the radicals are associated with the X radical and the hydrogen atom, and thus each of the compounds carry an OH or an COOH group; and the compounds may preferably be compounds such as octyl alcohol, dodecyl alcohol,

hexadecyl alcohol, octadecyl alcohol, octadecenyl alcohol, octylphenol, dodecylphenol, stearic acid monoglyceride, ricinoleic acid triglyceride, sorbitan oleate, sorbitan distearate, octanoic acid, dodecanoic acid, w-hydroxy decanoic acid, sebacic acid, aor w-dihydroxy octane, methylene bis-phenol and the like. This kind of compound may be an isolated one, or in the form of a natural mixture such as castor oil, tallow, fatty acid or the like.

The polyalkylene ether derivative usable in the present invention comprises a hydrophobic organic radical added with polyoxyethylene-, polyoxypropyleneor both. The degree of polymerization of the alkylene ether should preferably be 2-200, preferably less than 50. The polyalkylene ether derivative under consideration can be prepared easily by subjecting the hydrophobic compound carrying an OH- or COOH radical, in the form of one side starting material, with ethylene oxide or propylene oxide as the other side material.

The acrylic synthetic fiber according to this invention should preferably contain at least 2 wt. percent of the derivative relative to the polymer constituting the fiber. With a content considerably less than 2 wt. percent, the desired efiect would be insufiicient. The possible upper limits of the content depends naturally upon the kind and nature of the fiber, the method of preparation and the kind and nature of the polyalkylene ether derivative under consideration, the degree of the desired effect, and the like, and will amount generally to about There are various ways for the addition of the polyalkylene ether derivative to the acrylic fiber. As a measure, the derivative may be added to the spinning solution and the mixture is then spun into filamentary fibers according to a wet or dry spinning process, as the case may be.

The most preferable way for the addition of the polyalkylene ether derivative to the acrylic fiber is to immerse the? latter in an aqueous solution of said derivative. For this purpose, the acrylic fiber in a wet gel state is immersed, preferably at 20-30 C., in an aqueous bath containing the polyalkylene oxide derivative and then mangled or centrifuged at room temperature. When the derivative under consideration is liquid per se, the acrylic fiber in its wet gel state and the antistatic agent in the form of said kind of derivative may advantageously be brought into direct contact with each other. If the agent is insoluble in water, a solvent or dispersing agent may be adopted.

In any case, the contacting period between the fiber and the antistatic agent per se or in solution may extend from a shortest time such as one second to a considerable time lerigth such as several tens minutes. The bath may naturally contain one or more of various conventional fiberimproving additives. Anyhow, by adopting any one of the above-mentioned treating ways, the antistatic agent may be included within the fibers.

It will be seen from the foregoing that according to this invention a considerable amount of polyalkylene ether derivative is given in the body of the acrylic synthetic fibers. A most recommendable way for attaining this is such that a polymer comprising at least 70 wt. percent of polyacrylnitrile is wet spun into multifilaments which, in their wet gel state and subjected to a drying step, are brought into contact with said derivative by application thereof. By adopting this measure, considerably large quantity of said derivative can be applied to the fibers without any appreciable loss of the desirous textile characteristics such as favorable dyeing properties, dyeing fastness, strength, stretchability, hand feeling and the like.

In addition, the thus applied polyalkylene ether derivative is found to be highly durable to long extended boiling water treatment; dyeing treatment and repeated washings and laundering treatments. In these cases, a small part of the applied derivative or antistatic agent will be removed, but a substantial art th r f remains s a idue.

The fibrous material thus fed with the derivative shows a remarkable and so-to-speak a permanent antistatic property.

According to our practical experiments, we have found that the initial dosing of said derivative to the polyacrylic fibers, on the one hand, and the residual quantity of the derivative within the fibers as measured upon boiling water treatment, on the other hand, can be expressed by Way of example as shown in the attached drawing.

The initial dosing quantity mentioned throughout the present specification means such quantity of polyalkylene ether derivative which the fibers reserve therein upon the processing treatment according to the process of the invention, said quantity being measured relative to the dry weight of the material fibers.

The residual quantity in the above sense is that which is preserved upon a boiling water treatment extending for an hour. This quantity is also measured relative to the dry weight of the fibers. During said boiling treatment, a certain quantity of the derivative will be removed, but it has been found that still further appreciable removal will not generally be encountered, even when the fiber is subjected to further continued boiling treatment or to repeated washings and laundering treatments. As will be seen from the drawing, the residual quantity of the derivative will increase with an increase of the initial dosing. However, it should be noted that the residue rate (residual quantity/initial dosing) will decrease gradually. There will be a certain saturation value for a certain initial dosing. Beyond this value, an increase of the initial dosing 'will invite no appreciable increase in the residual quantity. This residual quantity may be called the saturated pickup and the initial dosing corresponding to this pick-up will be defined as the S-value throughout the specification.

The S-value is an adsorption equilibrium quantity which has however a certain margin depending upon the kind and nature of the fiber material polymer, derivative, the solvent and the spinning conditions. As a general measure, the S-value for acrylic fibers generally amounts to 5- 10%.

It has now amazingly been found that when the initial dose is smaller than the S-value, the desirous antistatic property will become very weak, while with the initial dose higher than the S-value, the antistatic performance of the treated fibers will be amazingly high. A preferred proeess according to the invention is based upon the above observation and is carried out advantageously so that the acrylic synthetic fibers of the above kind are treated with a polyalkylene ether derivative in such a way that the initial dose will amount to at least the saturated pick-up or adsorption value in the above sense. These saturated pickup or adsorption values can be easily determined by simple preparatory experiments.

Upon treatment of the fibers in the wet gel state in the afore-mentioned manner, the fibers are dried, thereby fixing the polyalkylene ether derivative in position within the interior of the mass of each of the fibers to a sufficient degree of washfastness, and indeed, without any substantial loss of the originally owned favorable physical and chemical properties.

In the case of the liquid treatment, the selection of the initial dose of the antistatic agent or polyalkylene ether derivative is made in consideration of the bath concentration and the liquid pick-up quantity by the wet gel fibers. The residual quantity of the antistatic substance in the body of the fibers may be controlled substantially exclusively by adjusting the degree of mangling or centrifuging in the above-menitoned sense. As an example, when the mangling or centrifuging is adjusted to provide a pick-up relative to the dry weight of the fibers upon im- When the principle of the invention is used in a continuous industrial process, the concentration of the treating bath must be higher than the initial dose, percent, relative to the wet gel filamentary fibers, preferably in the form of a tow, because the latter will introduce additional aqueous content to the bath composition. The fiber in its wet gel state will generally exhibit a 40 wt. percent, or higher, aqueous content, for instance, as measured directly after the spinning step of the fiber.

The conventionally employed stretching process may be carried out either in advance or after the contacting treatment of the fibers with the polyalkylene ether derivative.

durable to hot water treatment after finishing repeatedly applied washings and laundering treatments. Therefore, the amount of the incorporated polyalkylene ether deriva. tive can be preserved in a quantity substantially equal to the initial dose in the treated filamentary fibers-even upon frequently repeated laundering treatments. Thus, it may definitely be said that the antistatic performance of the acrylic fibers is improved in accordance with the novel teaching proposed by the present invention and is, so-tospeak, semi-permanent. j

The following, several preferred numerical examples will be given for a better understanding of the invention, wherein the antistatic performance of the fibers is given in each case in ohms by measurement of the characteristic surface resistance referred to briefly as resistance hereinafter, of a web composed of these fibers. The measurement was performed substantially as prescribed in the U8. Standards, AATCC 76-1964. The measuring instrument used for this purpose was a TR-65 Electrometer manufactured by Takeda Riken Kabushiki Kaisha, Tokyo. The measuring sample composed of well opened fibers, 2 gr The fiber cut length amounted to 6 cm. The sample container was a round cylindrical case of 50 cm., I.D., and having a 40 mm. height. A stationary cylindrical electrode was used, its 0D. being 40 mm.; and its thickness being 0.5 mm. The opposite movable electrode had an OD. of 40 mm. and a height of 30 mm. The resistance value was measured on an ohmmeter inserted in a measuring circuit including said two electrodes.

The relative humidity prevailing in the measuring chamber was maintained at 65%.

The judgement between the effectiveness and ineffectiveness of the desired antistatic performance was made in the following way: various fibrous webs of different resistance were shaped into respective threads from which knits were manufactured and tested upon wearing personally for the determination of the critical resistance value below which the unfavorable electrical discharge noises were not sensed by human ears. This critical value was found to be 10 ohms. Then, the sample webs were boilingly dyed and then subjected to 10 times repeated washingt'reatme nt s upon Meter. The dyed textile was then washed in a cold water bath for 5 minutes and then dried. It was assumed that this treatment corresponds to five regular washings.

EXAMPLE 1 An acrylonitrile copolymer comprising acrylonitrile 92.0 wt. percent, vinyl acetate 5.0 wt. percent and acrylamide 3.0 wt. percent, dissolved in dimethylformamide, was mixed with a compound corresponding to dodecyl phenol occupying 2.5 wt. percent of the polymer and with 180 mols of ethylene oxide, and the resulting mixture was intimately mixed together and dry spun into multifilaments from which a web was manufactured. Resistance of the web as formed, amounted to 7x10 ohms. After dyeing and 10 repeated washings, the web showed a resistance of 5 x 10 ohms.

As a comparative test, the resistance of a multifilament web admixed with none of the polyoxyalkylene ether derivative was measured under similar conditions and amounted to 4X 10 ohms. l

EXAMPLE 2 An acrylonitrile copolymer comprising acrylonitrile 91.7 wt. percent, methyl acrylate 3.0 wt. percent, acrylamide 5.0 wt. percent and sodium metallylsulfonate 0.3 wt. percent and dissolved in sodium rhodanate was mixed with a compound corresponding to octyl phenol which corresponds in turn to 6 wt. percent of the polymer and 2 mols of ethylene oxide, and mixed together intimately and then wet spun into multifilaments. A web manufactured therefrom showed in its resistance 2X10 ohms as spun. Upon being dyed and washed ten times, the web showed a resistance of 8X10 ohms.

As a comparative test, a similar web was prepared without addition of the polyoxyalkylene ether derivative thereto and showed a resistance of 8 X10 ohms.

EXAMPLE 3 A solution of the acrylonitrile copolymer of Example 1 dissolved in nitric acid, was mixed with a compound comprising dodecyl alcohol corresponding to 4 wt. percent of the polymer and added with 10 mols of ethylene oxide. The resulting mixture was mixed together evenly and wet spun to multifilaments. A web prepared therefrom showed a resistance of 2x10 ohms, and upon being dyed and washed 10 times 4X10 ohms.

As a reference, a similar web was prepared with no polyoxyalkylene ether derivative and the measured resistance was 6x10 ohms.

EXAMPLE 4 A solution of the same acrylonitrile copolymer disclosed in Example 2 in sodium rhodanate was mixed with a compound comprising polypropylene glycol corresponding to 7 wt. percent of the polymer and having an average degree of polymerization of 15 and 18 mols of ethylene oxide. The thus resulting mixture was mixed together thoroughly and wet spun to multifilaments. A web prepared therefrom showed a resistance as spun of 1x 10 ohms and upon being dyed and washed 10 times 9 10 ohms.

As a comparative test, a similar web was prepared,

without addition of polyoxyalkylene ether derivative thereto, whose resistance was 6X10 ohms.

EXAMPLE 5 f A solution of an acrylonitrile copolymer comprising acrylonitrile 89.5 wt. percent, methyl acrylate 5.0 wt.

percent, methyl methacrylate 5 .0 wt. percent and sodium parastyrenesulfonate 0.5 wt. percent dissolved in nitric acid was wet spun into multifilaments which were then washed and subjected to an 8-times elongation, so as to provide a multifilament tow in the wet gel state.

The tow was immersed in an aqueous solution of polyalkylene ether derivative for 30 minutes, the initial dosing being shown in Table I, squeezed, dried and then steamed at C. The filament had a mean denier of 3. The resistance and other properties of the web are shown in Table I.

TABLE I Resistance value, ohms Upon Initial dyeing and Elongadosing Rate of 25 times Tensile tion per- Sample designation rate, pick-up, Treated repeated strength, centage, of polyalkylene ether percent percent web washings g./d. percent Blank 7X10" 3X10 3. 5 28. 2

"A" 4. s a. 7 5x10 2x10 3. 6 29. 4 10. 1 6. 4 1X10 5X10" 3. 3 31. 5 14. 6 8. 1 3X10 9X10" 3. 2 33. 2 24. 7 8. 6 9X10 8X10" 2. 8 36. 1

"B" 3. 6 2. 8 2X10 7X10 3. 5 29. 6 9. 8 6. 2 7Xl0 2X10 3. 2 30. 6 15. 8. 0 0X10" 7X10 3. 1 32. 3 25. 7 8. 2. 8X10 6x10 2. 7 34. 7

"C" 4. 2 3. 7X10 3X10" 3. 6 29. 1 10. 5 6. 4 5X10 9X10 3. 4 31. 7 14. 5 7. 9 2X10 6x10 3. 3 32. 0 26. 4 8. 1 4X10 1X10 2. 9 35. 2

In the foregoing Table I, the derivatives AC repre- TABLE H sent the following compounds: Resistance value,

A Dodecyl alcohol added with mols of ohms ethylene ({Xlde. Initial Incor- Upon dyeing B Methylene-bis-phenol added with 5 mols pp y p rated and 25 times f l Sample designation of quantity, quantity, Treated repeated 0 propy eneoxl 6. polyalkylene ether percent percent web washings C Castor 011 added with 10 mols of ethy1- 2X10" 5X10 ene OX1 e. 7.9 6X10 3X10 8.4 1 10' 3 10 The dyeing was carried out using the cationic dyestufi 15.5 9.1 75210 n Astrazon Red RL (manufactured and sold by Farben- 3X10 8X10 fabriken Bayer AG, Leverkusen, Germany) in a quantity of 1% of the total weight of the fibers under boiling conditions for an hour, with a bath ratio 1:40.. Saturated absorption: about 8%. Initial supply quantity therefor (S- value): about 14%.

In the case of the antistatic agent A" with its initial supply quantity 10.1% and in spite of the existence of 6.4% of the antistatic agent within the fibers, the resistance values as measured upon spinning and upon washing treatments were substantially similar to those of the blank products, since the taken-up quantity was less than the said saturated value. On the contrary, with the initial dosing of 14.6%, the resistance as measured upon dyeing and repeated washes was rather low, representing a perman- Similar tows were prepared as in the foregoing Example 5. The remaining treatments were also similar to those .mentioned therein. The initial dosing amounted to about 15% of the saturation value.

In these tests, the derivatives D-G were as follows:

D Octylalcohol added with 2 mols of ethylene oxide. Dodecyl phenol added with 180 mols of ethylene oxide. Stearic acid added with 20 mols of ethyl- I ene oxide. Sorbitan oleate added with 13 mols of ethylene oxide.

EXAMPLE 7 TABLE III Test results are shown in Table II. Resistances were less than 10 ohms, which means a suflicient permanent antistatic performance.

In these samples, the saturating or saturated absorption amounted to about 6% and the initial dosing necessary therefor was about 11%.

With an initial dosing of 7.5%, the resistance values were substantially similar to those of the blank products since the dose was substantially smaller than the saturating threshold. With an initial dose of 11.0%, however,

10 erizable monomer is selected from the group consisting of methacrylic acid, butyl vinyl ether, acrylic acid ester, methacrylic acid ether, vinyl ether, vinyl acetate ester,

. styrene sulfonic acid, sodium styrene sulfonate, sodium allylsulfonate and sodium methallyl sulfonate.

the treated fibrous products showed a suflicient antistatic performance. 4. The process of claim 1 wherem said hydrophobic EXAMPLE organic radical is derived from castor oil, tallow or a fatty acid.

A solutlon of an acryioliltnle copolymer compnsmg 5- The process of claim 1 wherein said fibers are im- Percent acrylommle methyl ecu/late mersed in an aqueous solution of said derivative at a percent, acrylamide 5.0 wt. percent and sodium metallyltemperature of from to 300 and then centrifuged sulfonate 0.3 wt. percent, dissolved in nitric acid, was wet at room tamperamrfl p and then and Subjected a 700% 6. The process of claim 1 wherein said fibers are ditlon, so as to Prowde multlfilaments m the Wet gelhke rectly contacted with said derivative in liquid form. State" 15 7. The process of claim 1 wherein said fibers are im- These filaments were dipped for minutes in an aquemersed in an aqueous dispersion of said derivative. 011$ 8011mm confalmng compound which comprises 8. The process of claim 1 wherein said fibers in a gel Phenol added Wlth 10 111015 of Propylene QXlde and 15 state comprise fibers having at least a wt. percent mols of ethylene oxide, squeezed and dried. The multiaqueous content filaments, 2 denier P filament, in the form 0f a bundle, 20 9. In a process for producing acrylic syntheic fibers in- 75 denier, were processed to a plain weave fabric and the l di h Steps f; resulting resistance values were measured. The results are (1) forming continuous filaments by wet-spinning an shown in Table IV. acrylonitrile polymer selected from the group con- TABLE Iv Resistance value, ohms Initial Incorpoiil g ni i 5521 1 3 1? ti fi p e Sample designasupply rated times of filacentage of tion of polyalkyquantity, quantity, Treated repeated ment filament lene ether percent percent web washings yarn, g./d. yarn Blank 6X10 3x10 3.4 19,3

"H" 3.1 2.5 2x10 4x10 3.6 21,1 5.9 4.1 7 10 1x10 3.3 22.5

The embodiments of the invention in which an exsisting of a homopolymer of acrylonitrile and coclusive property or privilege is claimed are as follows: polymers of acrylonitrile with at least one unsaturated 1. A process for treating acrylic synthetic fibers to immonomer copolymerizable therewith, said copolymer part permanent antistatic properties thereto, said acrylic 40 containing at least 70% by weight of acrylonitrile; synthetic fibers being composed of a polymer selected (2) washing said continuous filaments; and from the group consisting of a homopolymer of acryloni- (3) drying the washed continuous filaments to produce trile and copolymers of acrylonitrile with at least one said acrylic synthetic fibers; unsaturated monomer copolymerizable therewith, said the improvement comprising producing synthetic copolymer containing at least 70% by weight acryloniacrylic fibers having permanent antistatic proptrile, said process comprising contacting said fibers which erties by contacting said continuous filaments, are in a gel state, prior to drying, with a first amount of prior to said drying step (3), which continuous at least one polyalkylene derivative represented by the filaments are in a wet gel state, with an aqueous formula: solution containing a first amount of at least one polyal-kylene ether derivative represented wherein R is a hydrophobic organic radical having from (oH,-oHR'-o H] 6 to 40 carbon atoms derived from a compound conm taining a OH or a COOH group, by removing said wherein R is a hydrophobic organic radical hav- -OH or said COOH, said compound being selected ing from 6 to 40 carbon atoms derived from a from the group consisting of octyl alcohol, dodecyl compound containing OH or a COOH alcohol, hexadecyl alcohol, octadecyl alcohol, octadecenyl group by removing said OH or said COOH alcohol, octylphenol, dodecylphenol, stearic acid monogroup, said compound being selected from the glyceride, ricinoleic acid triglyceride, sorbitan oleate, sorgroup consisting of octyl alcohol, dodecyl bitan distearate, octanoic acid, dodecanoic acid, u-hyalcohol, hexadecyl alcohol, octadecyl alcohol, droxy decanoic acid, sebacic acid, aor w-dihydroxy octadecenyl alcohol, octylphenol, dodecylphenl, octane and methylene bisphenol; R is hydrogen or stearic acid monoglyceride, ricinoleic acid trimethyl; X is O or CCO; n is an integer of 2-200 and m glyceride, sorbitan, oleate, sorbitan distearate, is an integer of from 1 to 6; said first amount being deoctanoic acid, dodecanoic acid, hydroxy determined by measuring, under the conditions of said concanoic acid, sebacic acid, or dihydroxy octane tactin g step, the maximum amount of said derivative which and methylene bisphenol; R is hydrogen or said fibers will adsorb and retain when the fibers are methyl; X is O or COO; n is an integer of 2- boiled in water for 1 hour, and then measuring the second 200 and m is an integer of from 1 to 6; said amount of said derivative which must be contacted with first amount being determined by measuring, said fibers to provide said maximum amount, wherein said under the conditions of said contacting step, the first amount is greater than said second amount. maximum amount of said derivative which said 2 The process of claim 1 wherein said maximum fibers will adsorb and retain when the fibers are amount varies from 5 to 10% by weight of said derivaboiled in water for one hour, and then measurtive, based on the dry weight of said fibers. ing the second amount of said derivative which 3. The process of claim 1 wherein said copolymmust be contacted with said fibers to provide 1 1 said maximum amount, wherein said first amount is greater than said second amount.

10. The process of claim 9 wherein said maximum amount varies from 5 to 10% by weight of said derivative, based on the dry weight of said fibers.

11. The process of claim 10 wherein said continuous filaments are subjected to a stretching step after said washing step and then subjected to said contacting step and then dried.

12. The process of claim 11 wherein said hydrophobic organic radical is derived from castor oil, tallow or a fatty acid. 13. The process of claim 11 wherein said washing step comprises washing said continuous filaments with water and wherein the temperature of said contacting step is from 20 to 30 C. and wherein after said contacting step, the resulting continuous filaments are centrifuged at room temperature.

12 References Cited UNITED STATES PATENTS 2,829,066 4/ 1958 Murdock 117-7 2,920,980 1/1960 Mooberry 117-65 2,965,678 12/1960 Sundbcrg 260-615 3,329,644 7/1967 Baur 26032.6

FOREIGN PATENTS 616,953 4/ 1962 Belgium 260 Dig. 17

OTHER REFERENCES Haye K. M.: American Dyestuff Reporter (June 7, 1954), pp. 368-371.

15 JOSEPH L. SCHOFER, Primary Examiner C. A. HENDERSON, 111., Assistant Examiner US. Cl. X.R.

26085.5 S, 88.7 B, Dig. 15, 17, 21; 264-178 F, 182

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