DE1669542A1 - Process for the manufacture of acrylic fibers - Google Patents

Description

Essen, the 18th October 1966

I- A r π μ r a N w a L γ (27 176 / La / th)

Dr. A η dreje w sk ϊ
4 J / s ^ en, Kettwiijer Str. 36

ι \ iu H im ι · Κ! ir ^ iof ■ lithtbuig)

Patent registration of the company
TOHO BEOLON KABUüHIKI KAISHA

6, Tori 3-chome, Nihombashi,
Chuo-ku,

Tokyo / - Japan -

Process for the production of acrylic fibers.

The invention is concerned with the production of polyacrylonitrile fibers by spinning and appropriate post-treatment and especially with the production of uniform and shrinkable acrylic fibers of improved composition. the It is a particular object of the invention to produce such acrylic fibers having a high degree of softness and excellent quality antistatic properties which remain semi-permanent while knitted from these fibers or Woven goods should have an excellent "handle" and a strong elasticity compared to full goods. aside from that is intended by the method according to the invention during spinning and the subsequent treatment for the production of acrylic fibers

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669542

the heat stretching and the heat relaxation by use a spinning solution which consists of a polymeric acrylonitrile with at least 85 percent by weight polyacrylonitrile and an aqueous saline solvent.

In its main features, the method according to the invention is for Manufacture of acrylic fibers from a spinning solution consisting of an acrylic polymer with at least 85 percent by weight Polyacrylonitrile and an inorganic aqueous salt solvent such as a concentrated aqueous solution mainly from zinc chloride, sodium thiocyanate or calcium thiocyanate, characterized in that the acrylic polymer is spun into a paser (aquagel tow) and washed for so long until the saline solvent is removed that the washed paser, the structure of which is essentially disordered, is brought into contact with an aqueous emulsion of a lubricant with one or more foam generators, wherein the paser absorbs at least 1.5 percent by weight of lubricant based on the dry weight of the resulting paser, and that the fiber treated with this aqueous emulsion is dried and partially or practically dry Conditions are stretched warm and relaxed when warm or fixed warm when stretched.

In particular, it is proposed that the aqueous inorganic salt solvent from an aqueous solution with 55-65 percent by weight Zinc chloride or a salt mixture of zinc chloride with an alkali metal chloride. The content of lubricant, which is absorbed by the staple fiber, is preferably 1.5-6% by weight based on the weight of the dry fiber. In particular, it is suggested that the spun and melted paser over 4 times in one

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Temperature stretched between 100 and 180 ° C and then relaxed in air or steam at a temperature of over 150 C. will.

The foam generators used for the lubricant can be cationic, anionic, nonionic or amphoteric Be kind. As a cationic foam generator, according to the invention, one or more such foam generators are made from a of the groups alkyl amine acetate, alkyl pyridine chloride, alkyltrimethyl chloramonium, N-alkyl-N-ethyl morpholine ethosulphate, Diethanolamine alkyl ester or its neutralization compound, to N, N'-ethyl-aminoethyl-alkylamide and alkyl-dimethyl-benzyl-ammonium chloride used whose alkyl radical has 5-20 carbon atoms. All foam generators are expedient from the group of sodium alkyl sulfate, polyoxyethylene alkyl sulfate ate, alkyl phosphate, sodium dialkyl sulfosuccinate, Sodium-alkyl-N-methyl-tauride and lI-methyl-glycine selected, the alkyl radical of which is preferably 5-20 carbon contains atoms. According to the invention, non-ionic foam generators are selected from the group consisting of polyoxyethylene alkyl esters, Polyoxyethylene-alleylamine, polyoxyethylene-alkylamide, polyoxyethylene-alkylaminoamide-sorbitan-mono-alkylate, Glycerine monoalkylate and the condensation compound of polyoxyethylene selected with polyoxypropylene, whose alkyl radical is preferred Has 5-20 carbon atoms. Amphoteric foam generators are, however, from the group N-alkyl-N-dimethyl-betaine and l-hydroxyethylene ^ -alkyl ^ -lmidazoline selected, whose alkyl radical preferably has 5-20 carbon atoms.

As is well known, in the manufacture of acrylic fibers, the peeling is usually done on the warm stretched or warm ones stretched and warm relaxed Pasern performed, their

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1G69542

Molecular structure is substantially or at least partially aligned. Most of the lubricant, which is applied to the fiber, remains on the fiber surface and can be removed with a warm mixture of alcohol and gasoline without any particular difficulty.

In general, a lubricant additive of 0.2-0.6 is used Weight based on the dry fiber as appropriate deems. Since the purpose of the previous Schmälzen is mainly the physical properties the fiber surface such as its antistatic Improve properties and their coefficient of friction, there was previously no practical need to add a noticeable amount of lubricant over 1% by weight to the fiber structure to penetrate.

The use of lubricants in the manufacture of synthetic fibers has actually not been done in any way other noticeable effect expected than the improvement in practical properties of the fiber surface.

In contrast to this normally customary process, according to the invention, the melting on the spun and watered Fibers carried out, which have not yet been stretched warm and whose structure is still practically tangled, with the through the amount of lubricant absorbed by these fibers is controlled to be at least 1.5% by weight based on the dry fiber. Here, the melting is usually carried out in such a way that the fibers are in intimate contact with an aqueous one Emulsion of a synthetic foam generator, the fiber containing a significant amount of the foaming agent can absorb anything in such a short time as

.8AD, ORIGINAL

can take place under a minute, since the fiber structure is still is not ordered, i.e. still confused. The absorbed lubricant, i.e. the foam generator, can in this way be fed into the Disordered fiber structures penetrate and form an acrylic fiber of a new composition.

The amount of foam generator to be absorbed can easily be controlled by adjusting the concentration, i.e. the Content of the foam generator in the aqueous emulsion selected and adjusted accordingly and the emulsion temperature and the contact time of the fiber with the emulsion is regulated, albeit often the affinity or tendency of the foam generator to absorb with respect to the acrylic fibers depends on the chemical composition or the molecular weight of the foam generator.

The invention is based on the unexpected finding that such a special peeling treatment facilitates the subsequent hot stretching and hot relaxation, and that from such acrylic fibers knitted and woven goods receive an excellent "handle" and in comparison to Woolen goods are very elastic and retain their good fit and fit for a long time.

The acrylic fiber melted by the method according to the invention, which has absorbed a considerable amount of the lubricant can easily be reduced to a lower one Temperature and stretching warm to a greater extent than an acrylic fiber without such a peeling treatment, even if the fiber is practically dry and then stretched warm in dry air. A special effect this absorbed foam generator is particularly evident in

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Relax the warm, stretched paser in heated air or under steam at atmospheric pressure, as there is an increasing proportion of the foam generator or lubricant the maximum shrinkage in the fiber upon relaxation at a given temperature and within a given Period of time increases significantly respectively. the relaxation for one given shrinkage can be performed at a lower temperature or within a shorter time.

Numerous examples showing these effects are shown in Tables 2 and j5.

Surprisingly, it was also found that the spun by the process according to the invention and then post-treated fibers had a fuller feel than those produced by previously known processes and that knitted and woven fabrics made from such acrylic fibers are excellent as compared with woolen fabrics "Hand" and high elasticity, and that the original condition even after repeated washing and drying again of the pastes and woven or knitted goods hardly suffered compared to such goods made of acrylic fibers of the type known up to now would have. In the method according to the invention, most of that which has penetrated into the moist, gelatinous paser structure is Lubricant when drying these fibers in hot air or when hot stretching at temperatures above about 8o ° C absolutely fixed and can even with warm alcohol-Benz in mixtures cannot be extracted. This fixed lubricant is hereinafter referred to as "inner oil". It It can be assumed that the aforementioned effects of the method according to the invention are directly or indirectly due to the presence this "inner oil" depends. That so far

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customary sizing of the hot-drawn and, if necessary On the other hand, the lubricant absorbed by these fibers from warm relaxed fibers remains for the most part on the fiber surface hanging and can therefore be easily washed off with a warm mixture of alcohol and gasoline. The following Table 1 shows some typical results of "inner oil" and "surface oil" on acrylic fibers, which BEZW after the inventive method. were produced by conventional methods, in the latter case the proportion of "inner oil" assumed as the difference between the total amount of oil and the amount of "surface oil" became. The amount of total oil was determined by measuring the actual consumption of lubricant per unit weight of the fiber, taking into account the loss of material Test measured and the amount of "surface oil" was extracted with a hot alcohol-gasoline mixture determined in a ratio of 1: 2.

As shown in Table 1 below, the amounts of "surface oil" in the case of fibers according to the process according to the invention, approximately the same amount is present as in the case of fibers which were produced according to the usual methods, while the differences in the amount of "inner oil" absorbed are very considerable in both procedures. It was also found that during further processing of the acrylic fibers produced and treated according to the invention, the proportion of the inner oil did not cause any disturbances.

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Tabel

Lard Treatment Trial "Total Oil."

Surface oil

inner oil "

Immediately after washing the spun fiber (invention)

1 1 , 85 Weight % 2 2 , 56 It 4th , 50 It 4th O , 18 Weight % 5 0 , 25 dd 6th 0 , 50 It

0.21 wt- # 1.64 wt-: 0.12 "2.24" 0.40 "4.10"

After hot stretching and warming, tensioning (previously common)

0.16 wt- # 0.02 wt-J 0.22 "0.03" 0.49 "0.01"

Pipes produced by the method of the invention can therefore be subjected to the subsequent further treatment required in each case, i.e. cut directly, turbo-nimble and spun. It is every now and then determine that the amount of "surface oil" which is present in the process of the invention when smelting is not sufficient to be able to spin the pasers directly in spinning machines into high-quality yarns. In this case is expediently the Paser again after the hot stretching and the warm relaxation brought into contact with an aqueous emulsion of a sea malting agent so that the amount of the "surface oil" absorbed reaches the desired value.

BATH ORIGINAL

: ο

As already mentioned, the hot stretching after Drying of the damp acrylic fiber and subsequent warm relaxation relieved if the fiber to be warm drawn has a significant amount of "inner oil". Some examples the effect are shown in Tables 2 and 3 below. Table 2 shows that determined by experiments Relationship between the total amount of oil and the maximum hot stretch, with the acrylic sample strands after a wet spinning process using an aqueous one Zinc chloride solution prepared and placed in hot air before Hot stretching were dried. Table 2 shows the maximum shrinkage obtained for each of the hot drawn ones Cable strands were measured according to each of the test numbers according to Table 2, with the hot relaxation in Steam was conducted at atmospheric pressure at a temperature close to 240 ° C. From the data set out in these tables The results clearly show that the maximum hot stretching and the maximum shrinkage during hot relaxation following the stretching, with increasing amount of the "total oil" or, more correctly, of the "inner oil" gain weight.

template

Table 2 Maximum warmth "Total oil" 350 % 0 wt -.% 450 % 1.5 " 580 % 3.0 " 600 % 5.1 "

/ 1922

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Tabel ?

Pattern Maximum shrinkage AI 10 %

BI 24 %

B - 2 30 %

B - 3 kO%

In practice, the hot stretching is around 4 times a temperature between 100 and 180 ° C and the following Warm relaxation at a temperature above 150 C for the production of acrylic fibers of high bulk as well as good mechanical ones Features extremely functional.

The quality features of the woven and knitted goods produced from the acrylic fibers by the method according to the invention have already been mentioned. Such quality designations as "excellent handle" and "high elasticity compared to that of woolen goods ¹¹ are not quantitative but rather subjective and emotional. It would therefore be very desirable to create a test method by which the results of the method according to the invention in relation to the The quality of the finished goods could be quantified, however, since there is still no instrumental method to test how to quantify the "feel" and the "elasticity" of knitwear and woven goods, a number of professionals who have had good experiences in the quality inspection of fiber ^ rare have requested an inspection.

¹⁰ '^ 922 ORiGlNALINSPECtED

The implementation of this test and a typical result with regard to the effect of the method according to the invention will be explained in Example 2 below.

It has also been found that a desirable shrinkable (Shrinkable) fiber can be produced in that the produced by the process according to the invention even or smooth acrylic fiber strand further post-treatment is subjected. ,

As is well known, shrinkable acrylic fibers can be produced by warm stretching a uniform acrylic fiber strand again in the dry state, which process, in contrast to the first warm stretching carried out in the production of the smooth fiber strand, is referred to as "second warm stretching", whereupon the fiber strand is then referred to immediately cooled in a stream of air under tension and, if necessary, cut. The shrinkage measure, which is measured as the measure of the shrinkage of the fiber length in boiling water or steam at 100 ^° C., generally increases with larger values for the second drawing, but an increase in the ratio leads to a decrease in the knot strength and elongation of the knot finished fibers results in what is by no means desirable from the point of view of the production of flawless shrinkable yarns. Since the industrial very shrinking process with a smooth or roller carding machine requires a lower limit for the knot strength or knot elongation in order to achieve good shrinkable yarns, there is an upper limit for the second stretching, so that the shrinkage value is limited in practice.

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When producing smooth acrylic fiber strands by the method using an aqueous solvent such as an aqueous concentrated solution of zinc chloride, thiocyanate or nitric acid, the tensile strength and the knot elongation of the fibers tend to decrease more by the second drawing than the acrylic fiber strands which are used an organic solvent such as dimethylformamide, so there has been a desire for an improved process by which the shrinkable fiber of a given shrink value could be made with little second draw. Tests have shown that the process according to the invention meets these requirements. The percentage shrinkage of the shrinkable fiber produced from the uniform fiber strand according to the invention is 2-10 # higher than that of conventional shrinkable acrylic fiber strands. If, for example, a 1.3-fold stretching was set for the second stretching, the shrinkage of the staple fiber after cutting the acrylic fiber strand according to the invention was 14-15 %, but only 9-12 # for staple fibers from one fiber strand up to now customary process was produced. When the fiber was stretched 1-4-1.5 times in the second stretching, a shrinkage value of 21-2k% for the staple fibers and a knot strength of 1.5-1.6 g / denier for the acrylic fibers after the Invention can be achieved, while the shrinkage value for staple fibers was only Ik -16 # according to the usual methods.

In the manufacture of shrinkable acrylic fibers, it has been found that that weak relaxation under steam is very effective in improving the evenness of the shrinkage, if the average shrinkage is also somewhat reduced in accordance with the extent of relaxation used.

This result is of great importance, since the fluctuation in the shrinkage of the yarn in the case of shrinkable yarns largely depends on the fluctuation in the shrinkage of the material fiber. The size of 6 ~ shrinkage (copulation standard deviation) for a number of shrinkable acrylic fibers is greatly reduced when a weak steam relax by 2 subsequent to the second drawing the fiber strand - is subjected to $ 6. For example, the average very shrinkage value and the value <3 ~ in % for a shrinkable acrylic staple fiber after the second stretching is 1 - 4 times as much as $ 25 or. 5.1 % if this relaxation is not performed. In contrast, with a vapor expansion of k% , these values are respectively 21%. 0.9%. The same values for the second stretch are 1.5 times without relaxation j50 and / or. 3 »3 %» while with a vapor relaxation of 6% the corresponding values 2k% respectively. 1.4 #. In all of these tests, the pas strand produced by the process according to the invention contained 3 * 5% by weight of "inner oil".

Lubricants that can be used in the process according to the invention cationic, anionic, non-ionic or amphoteric Use foam generators, as has already been explained in detail at the beginning. A mixture of use at least two foam generators from any of these four groups. Often there will be a mix of at least two different types of foam generator are used, but a combination of a foam generator from the cationic Group with a foam generator from the anionic or amphoteric group and a combination of an anionic group Foam generator with an amphoteric foam generator is not permitted.

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In the method according to the invention, at least 1.5 Ji by weight of the foam generator or foam generators based on the dry fiber into which the moist, not yet molecularly ordered fibers are absorbed.

The absorption proportion is preferably between 1.5 and 6 Weight, albeit strictly speaking the chemical composition, the molecular structure and the molecular weight of the foam generator influences these effects to some extent. A proportion of 2.5-4.5 is preferred Weight- ^ reached.

The invention is particularly tailored for use in methods of making acrylic fibers in which one aqueous inorganic salt solution, which zinc chloride or an alkali or alkaline earth metal salt of thiocyanic acid as Main component contains, used as a solvent for the fiber-forming acrylonitrile polymer or the copolymer will. Is preferred for the aqueous salt-containing solvent Zinc chloride alone or a mixture of zinc chloride with a chloride of an alkali or an alkaline earth metal used, the total salt content being preferred 55 - 65 weight ^ is.

The acrylonitrile polymer used in the invention is Polyacrylonitrile and any acrylonitrile interpolymer with at least 85% by weight of polymerized acrylonitrile and up to 15% by weight of another monomer or other Monomers which can be copolymerized with acrylonitrile, such as methyl acrylate, methyl methacrylate. Vinyl acetate, Acrylamide-styled sulfonate, allyl sulfonate, methallyl sulfonate, acrylic or methacrylic acid, itaconic acid, vinyl pyridines and vinyl imidazoles.

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The invention and its effects are illustrated below some examples are explained further.

Example 1;

A spinning solution consisting of 90 parts of a salt-containing solvent with 53 wt .- ^ zinc chloride, 4 wt -.% Sodium chloride and 43 wt -.% Of water and 10 parts of an acrylonitrile copolymer with 92 parts by weight JSS acrylonitrile and 8 wt. - ^ Methyl acrylate was spun through a spinneret with 6000 holes into a precipitation bath, which contained an aqueous salt solution which was obtained by diluting the salt-containing solvent to a concentration of 20.

The soft cable (aquagel tow) pulled out of the precipitation bath $ Μ $ 10 (£ ΚΧΧ] α5) Ε $ was washed in water until it was practically free of zinc chloride, whereby it was warped 2.5 times in the water baths make washing out easier. This washed out soft cable was 15 see. immersed in an aqueous emulsion at 40 ° C, which contained 30 g of diethanelamine mono-ester of phosphate of lauric acid per liter, whereupon it was squeezed out with pressure rollers and dried. The dried tow containing 1.5 wt -.% Of lubricant. Subsequently, it was heated at 150 ° C to 5.2 times trekked and then immediately relaxed to # 30 in superheated steam at 200 ⁰ C, then cooled and crimped. The wire harness then contained 0.2 wt .- # "surface oil" and 1.3 wt .- # "interior oil".

Knitwear made of this material had an excellent one "Grip" and strong elasticity compared to woolen goods. Even after washing and drying several times

her excellent "grip" hardly changed. For acrylic fibers, which do not have any noticeable "inner oil" content, I did not have such good results ascertained.

Example 2:

In experiment A, the soft fiber tow produced under the same conditions as in Example 1 was first washed in water, squeezed out and dried, then for 20 seconds. immersed in an aqueous emulsion at 45 ° C, which contained 30 g of polyoxyethylene lauryl amine and 30 g of diethylaminoethyl stearyl amide per liter. It was then squeezed out again and dried. The dry Paserstrang contained a total of 3 * 5 wt -.% Of the above Schmälzmittelmischung. This was stretched at 150 ⁰ C to 5 times, laid in superheated steam of 200 ⁰ C and then brought into contact with an aqueous emulsion of polyoxyethylene alkylamine, such that 0.1 wt -.% Of alkylamine in addition to the Paseroberfläche stuck. The total amount of "surface oil", consisting of polyoxyethylene alkylamine and diethylaminoethyl oleic acid amide, was 0.35% by weight based on the knitwear made from the fibers, which had a very wool-like feel.

In Experiment B, the soft fiber strand obtained under the same conditions as in Experiment A was washed and then washed stretched 5 times in hot water of 90 - 95 ° C, in relaxed boiling water, then expressed between pressure rollers and then 2 see. with an aqueous emulsion brought into contact, which per liter 7 g polyoxyethylene

·? ·>. BADORIGfNAL

Alkylamine and 7 g of diethylaminoethyl-oleic acid amide, and expressed again. This moist filament strand was then dried under very little tension accompanied by a further relaxation, heat-set and subjected to a second fatliquoring or smelting with alkylamine and finally dried. In this experiment, the relaxation was brought to the same total value as in experiment A, and the two lubrications were also controlled in such a way that the amount of "surface oil" finally came to close to 0.35. -% was. The Paser spun well, but the one from it

was

The quality of the knitwear produced is poorer than in experiment A.

Then 5 sample strands were made, the different Amounts of lubricant contained, using the same experimental conditions as were observed before, with the exception of the fact that in each sample the first enamel bath is a different one Had lubricant concentration. These different strands of pas were made while observing the same working conditions five puffy sweaters were made, for which purpose the yarns were made using the turbo process. The knitting pattern as well as the number of yarns and the shrinkage value were of course the same for all five patterns. These patterns were then by 10 examiners who test knitted and woven goods Possessed a great deal of experience, checked, whereby it was mainly on the determination of the "handle" etc., so the wearing properties arrived. The results of this test are shown below Table J. An additional experimental test showed that the judgments "Excellent" and "Very Good" matched almost exactly the judges' verdicts on similar sweaters from 100 # Wool matched.

10i / 1922

Table 3 :

1 2 3 4th 5 - 1 Pattern No: 5 Total amount of oil 0.36 1 2 3.5 4.5 in the paser 0 (in wt .- ^) 0 judgement (Number of inspectors) 0 0 1 8th Outstanding 0 0 3 2 very good 0 1 5 0 Good 3 β 1 0 middle 7th 3 0 0 Bad Example 3:

9 parts of a copolymer of 92 wt .- ^ acrylonitrile and 8 wt -.% Of methyl methacrylate were dissolved 91 parts by weight of an aqueous salt-containing solvent of 42 wt .- ^ zinc chloride, 16 wt .- # potassium chloride and 42 wt .- # water.

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This polymer solution was then in a precipitation bath consisting of a 25% aqueous solution of the salt-containing Solvent spun out through spinnerets. The fiber strand coming out of the felling bath was thoroughly countercurrent washed out with water, then squeezed out and immersed in a lubricating bath, which is an aqueous emulsion with 20 g / l di-lauryl phosphate sodium salt, 20 g / l polyoxyethylene stearic amide and 30 g / l polyoxyethylene-polyoxypropylene block polymer contained.

The fiber strand was then dried, ^{stretched 5.5 times warm at 150 °} C. and immediately thereafter relaxed again by 35 °, based on the length of the stretched strand, in superheated steam at 250 ^{° C.} The finished fiber contained 4.5 wt .- # of lubricant in the dry state. The goods knitted and woven from these fibers were superior in wear and antistatic properties to knitted and woven goods made from acrylic fibers without any noticeable amount of any lubricant.

Expectations;

1 L

Claims (12)

. · Η ■ Ί 669542 claims. 1. A process for the production of acrylic fibers from a spinning solution consisting of an acrylic polymer with at least 85 percent by weight polyacrylonitrile and an inorganic aqueous salt solvent, characterized in that the acrylic polymer is spun into a fiber (aquagel tow) and washed until the salt solvent is removed; that the washed fiber, its structure is substantially disordered, is brought into contact with an aqueous emulsion of a lubricant with one or more foam generators, the fiber at least 1.5 percent by weight of lubricant based on the dry weight of the resulting fiber, and that the fiber treated with this aqueous emulsion is dried and in a partially or practically dry state when stretched and relaxed warm or fixed warm when stretched. 2. The method according to claim 1, characterized in that the aqueous inorganic salt solvent from a aqueous solution with 55 - 65 weight # zinc chloride or a salt mixture of zinc chloride with an alkali chloride or an alkali metal chloride. 5. The method according to claim 1 or 2, characterized in that that the content of lubricant, which is absorbed by the staple fiber, 1.5-6 percent by weight based on the Weight of the dry fiber. 4. The method according to any one of claims 1-3, characterized in that the fiber over the 4-fold is stretched at a temperature between 100 and l8o ° C and is then released in the air or steam at a temperature of about 150 ⁰ C. 1 C 5. The method according to any one of claims 1-4, characterized in that the lubricant has one or more cationic foam generators from the group consisting of alkyl amine acetate, alkyl pyridine chloride, alkyl trimethyl chloramonium, N-alkyl-N-ethyl Morpholine ethosulfate, diethanolamine alkyl ester or its neutralization ^{compound, contains up to N, N 1} -ethyl-aminoethyl-alkylamide and alkyl-dimethyl-benzyl-ammonium chloride, the alkyl radical of these compounds having 5-20 carbon atoms. 6. The method according to any one of claims 1-4, characterized in that that the lubricant is one or more anionic foam generators from the group consisting of sodium alkyl sulfate, polyoxyethylene alkyl sulfate, Alkyl phosphate, sodium dialkyl sulfosuccinate, Sodium-alkyl-N-methyl-tauride and N-methylr-glycine contains, the alkyl radical of which is preferably 5-20 carbon atoms owns. 7. Method according to one of claims 1-4, characterized in that that the lubricant has one or more non-ionic foam generators from the group consisting of polyoxyethylene alkyl esters, Polyoxyethylene alkylamine, polyoxyethylene alkylamide, Polyoxyethylene-alkylaminoamide-sorbitan-mono-alkylate, glycerine-mono-alkylate and the condensation compound of polyoxyethylene with polylxypropylene contains their alkyl radical preferably has 5-20 carbon atoms. 8. The method according to any one of claims 1-4, characterized in that that the lubricant has one or more amphoteric foam generators from the group consisting of N-alkyl-N-dimethyl-betaine and Contains l-hydroxyethylene-2-alkyl-2-imidazoline, the alkyl radical of which preferably has 5 to 20 carbon atoms. 101/922 1689542 9. The method according to any one of claims 1-4, characterized in that a mixture of as lubricant at least two foam generators from the groups specified in claims 5 and 7 is used. 10. The method according to any one of claims 1-4, characterized in that a mixture of as lubricant at least two foam generators from the groups specified in claims 6 and 7 is used. 11. The method according to any one of claims 1-4, characterized in that a mixture of as lubricant at least two foam generators from the groups specified in claims 7 and 8 is used. 12. The method according to any one of claims 1-4, characterized in that a mixture of as lubricant at least two foam generators from the groups specified in claims 5, 6 and 7 are used. 13 · Process for making shrinkable fibers, thereby characterized in that the endless fiber produced by one of the methods 1-12 is in a practically dry state stretched warm and then relaxed by 2 - 6 # of its length. Patent attorney Dr. W. Andreevsky. 109/1922