US3436169A - Continuous dyeing of acrylic fiber material - Google Patents

Description

United States Patent 3,436,169 CONTINUOUS DYEING 0F ACRYLIC FIBER MATERIAL Jakob Zurbuchen, Basel-Land, and Jakob Bindler, Riehen, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Continuation-impart of applications Ser. No.

373,053, and Ser. No. 373,054, June 5, 1964. This application Dec. 2, 1965, Ser. No. 511,238 Claims priority, application Switzerland, June 11, 1963, 7,282/63, 7,283/63; Dec. 10, 1964, 15,954/64, 15,955/ 64 Int. Cl. D06p 3/76, 3/70 US. Cl. 855 35 Claims This application is a continuation-impart of our pending patent application Ser. Nos. 373,053 and 373,054, both are now abandoned, both filed on June 5, 1964.

This invention relates to the continuous dyeing of acrylic fiber materials. Continuous dyeing of such fibers has, to our knowledge, not been carried out in practice in the past with satisfactory results, namely affording level, fast dyeings on such materials with good color yields, and free from the undesirable sandwich effect.

It is known that polyacrylonitrile fibers and the like materials of acrylic fibers are dyed with basic dyestuffs having affinity for the aforesaid fibers batchwise in an exhaustion process (goods-to-liquor ratio above 1:5) at pH values within the range of 4.5 to 5.5, with the aid of anion-active or cation-active auxiliary agents which serve as retarders to counteract the tendency of the aforesaid basic dyestuffs to draw too rapidly from the dyebath onto the acrylic fibers, and to prevent lack of uniformity of the dyeings.

Purely non-ionogenic auxiliaries, on the other hand, have been used only in known processes for the dyeing of polyamide fibers as retarding agents to attain lighter shades, and for the removal of dyestuff from the dyed fibers in the case of insufficient fastness of the dyeings, especially crocking.

The pad dyeing of polyacrylonitrile and the like acrylic fibers, especially in the form of rawstock tows and unrelaxed and steam-relaxed tops which are suitable as starting materials for the manufacture of yarns, encounters considerable difficulties. In pad-steaming tows of acrylic fibers, it has been necessary to use as dye assistants in particular ethylene carbonate and the like cyclic ester, in a buffered acetic acid medium at the pH range in the vicinity of 5. However, the resulting dye ings often show the so-called sandwich effect, unlevelness and a relatively fiat, undesirable handle. Blocking out of certain dyestuffs in the conventionally used dyestuff mixtures, with excessive loss of dye in the rinse and decreased fastness may also result.

It has further been proposed to produce dyeings with basic dye-stuffs on blended fabrics of wool and acrylic fibers by pad-dyeing with a dye liquor thickened with sodium alginate, and having a substantially neutral pH, in the range above 6, and preferably at about 7, as dye assistants in lieu of ethylene carbonate.

The pad-liquors in this known process have, however, a tendency to flocculate, which leads to streaky dyeings. Moreover, the yield of dyestuff on the fiber is often unsatisfactory and the textile products, especially acrylic fiber tops dyed in this manner also show a flat handle lacking in volume. A handle 'of satisfactory volume or loftiness is, however, highly desired, for it is known by experience to lead to better spinnalbility of the tops and better performance of the tow during cutting into staple fibers, for instance in a turbo-stapler, for the purpose of making tops or spun yarn.

Moreover, a voluminous handle of textile acrylic fibers is of great importance for their further processing in the Patented Apr. 1, 1969 manufacture of high bulk yarns therefrom, which latter serve especially in the manufacture 'of pullovers and the like textile garments.

The term acrylic fibers as used in this specification and in the appended claims means pure acrylic fibers as defined, for instance, by P. W. Sherwood in Modern Textiles, 44, March 1963, reported in American Dyestuff Reporter of June 10, 1963 pages 32 (437) et seq., in contrast to modacrylic fibers defined ibidem. Among the most important acrylic fibers are Orlon, which is nearly pure polyacrylonitrile eopolymerized with a small amount of acrylic esters or styrene sulfonic acid, and Acrilan, which contains well in excess of of acrylonitrile together with vinyl pyridines such as methyl vinyl pyridine or other vinyl pyridines listed, e.g. in Canadian Patent 557,597, and containing acid group dyesites.

It is, therefore, an object of the present invention to provide a continuous dyeing process, preferably by pad steaming, for acrylic fiber materials such as rawstock, tows and fabrics, and, especially, however, acrylic fiber tow or tops destined for the manufacture of high bulk yarns, whereby dyed materials are produced which are distinguished by deeper shades, freedom from sandwich effects and uniformity of shade, especially, also, when dyeing is carried out with dyestuff mixtures, and which, especially in the case of tops and tows, are distinguished by a loftier, more voluminous handle.

This and other objects which will become apparent as the description of the invention proceeds, are attained by a process for the continuous dyeing of polymeric and copolymeric acrylonitrile fibrous material which comprises, according to a first aspect of the invention, using a dyestuff preparation consisting of optionally thickened aqueous, acid solution of basic dyestuffs, soluble salts of saturated carboxylic acids having 8 to 14 carbon atoms and surface active hydrophilic to water-soluble polyglycol ethers having lipophilic radicals, and sufficient amount of a water-soluble strong, preferably organic acid, especially an acid as defined in detail hereinafter, to make the pH of the preparation 2 to, at most, 4.3 and preferably 2.5 to 4.0 and which preparation can contain other auxiliaries, particularly amides of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms with primary or secondary alkanol-amines. The goods are impregnated with these preparations at temperatures lying below the drawing temperature of the dyestuffs and then subjected to moist heat treatment by the usual methods.

The acidity of the impregnating liquor is brought about by adding thereto organic acids as defined above, particularly odorless lower alkanoic acids such as acetic acid or formic acid, but also such industrially available acid as tartaric acid. These are added in amounts of 30 to 300 g. and, preferably, 40 to 60 g. per liter of impregnating liquor in order to ensure that the pH of the liquor is below 4.5, preferably between 2.5 to 4.0. Strong acids being suitable in the processes according to the invention are those, the pK value of which for at least the first hydrogen is below 5.

This high acidity of the impregnation liquors according to the invention or dyestuff-dye carrier pastes used for their preparation is a very important feature of the invention.

Hitherto, when no acid at all or considerably smaller amounts of acid were used, e.g. in concentrations of 2 to 6 g. per liter, low color yields were obtained, the dyeings showed pronounced sandwich effects, or the dyestuffs were partially destroyed, leading to undesirable shifts in shade, especially in the dyeings of some types of acrylic fiber materials, particularly from among those having carboxyl groups as dyesites, which tend to split off alkali when treated with boiling dye liquors.

The impregnating liquors according to the first aspect of the invention contain as salts of suitable saturated carboxylic acids having 8 to 14 carbon atoms, especially the salts which are more specifically described hereinafter under the first preferred mode of carrying out this aspect of the invention in practice.

As surface active, hydrophilic to Water-soluble polyglycol ethers containing lipophilic radicals according to the invention, the dyestuff preparations according to the invention contain polyglycol ethers, particularly ethylene oxide condensation products of alkyl phenols containing one or more alkyl substituents which together contain at least 8 carbon atoms; of primary or secondary, monoor poly-basic aliphatic and cycloaliphatic amines containing at least one higher alkyl or alkenyl radical having at least 8 carbon atoms, or of alkanaolamines containing such lipophilic alkyl and aralkyl radicals; and also ethylene oxide condensation products of alkanolamides, aminoalkylamides and aminoalkyl esters of higher, aliphatic carboxylic acids and higher alkylated alkylaryloxy carboxylic acids, into all of which ethylene oxide condensation products can be built individual substituted epoxides such as styrene oxide and/ or propylene oxide.

The amount of auxiliaries mixture per liter of dye liquor is, e.g. 2 to 100 g. and, preferably, to 40 g.

The weight ratio of the soluble fatty acid salt to the polyglycol ethers according to the first aspect of the invention should be smaller than 3:1 and preferably at about 2:1 to 1:2. When mixtures containing the salts mentioned, polyglycol ethers and amides are used, then the ratio by weight of the said salts to the polyglycol ether/ amide mixture is smaller than 3 :1 and preferably in the range of 2:1 to 1:8.

As basic dyestuffs, dyestuif preparations according to the invention contain conventional salts and metal halide, e.g. zinc chloride, double salts of known cationic dyestuffs, in particular of methine or azamethine dyestuffs which contain the indolinium, pyrazolium, imidazolium, triazolium, tetrazolium, oxdiazolium, oxazolium, thiazoliurn, pyridinium, pyrimidinium, pyrazinium ring. The heterocycles mentioned can optionally be substituted and/ or condensed with aromatic rings. Also, cationic dyestuffs of the diphenylmethane, triphenylmethane, oxazine and triazine series can be used and, finally, also color salts of the arylazo and anthraquinone series having an external onium group.

Thickeners suitable for use in an acid bath are, e.g. the soluble types of gum usual in the textile industry, e.g. so-called crystal gum or thickeners having a cellulose basis such as locust bean flour, tragacanth, British gum or cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose. Locust bean flour thickeners and galactomannan thickeners are preferred.

As other auxiliaries usual in the dyeing industry, the impregnating liquor can contain, e.g. organic solvents, in particular ethylene glycol monoethyl ether or thiodiethylene glycol and also ethylene carbonate.

Polymeric or copolymeric acrylonitrile fiber materials suitable for dyeing by the process according to the invention are acrylic fibers, i.e. fibers of which 8010'0% consists of polymeric acrylonitrile, and which contain acid dyesites, more particularly sulfonic acid and/or carboxylic acid dyesites.

The acrylic fiber can be dyed according to the invention in any form desired, e.g. in the form of rawstoc-k material, yarn or fabrics, particularly however in the form of tow or slubbing.

The fibrous material is impregnated, for example, by printing, coating or spraying, preferably however, by pad dyeing in the foulard.

The impregnating liquor according to the invention is advantageously produced by pasting the basic dyestuff with the amount of acid used, particularly with the required amount of acid, preferably a 6080% acetic acid being used, adding hot water to the paste and then adding the salts and polyglycol ethers as well as, optionally, other auxiliaries usually employed in the dyeing industry.

The polyacrylonitrile fibers are advantageously impregnated at 30 to C. and then squeezed out to leave on the fibers the desired content of impregnating liquor of about m 130% calculated on the dry weight of the fiber material.

The impregnated fibers are then steamed by the usual methods, advantageously with neutral saturated steam, or, preferably, slightly overheated steam.

The dyed and steamed goods are subsequently rinsed, advantageously with cold or warm water which can contain the additive usual in the dyeing industry, e.g. formic acid or acetic acid or also substances rendering the goods antistatic or fabric softeners.

By the process according to the invention, particularly in the continuous dyeing of polymeric and copolymeric acrylonitrile fibers, very deep shades free from sandwich effects are obtained which are distinguished by the evenness of the dyeing. In particular, in the preferred continuous dyeing with a mixture of difierent basic dyestufls, there is no selective dyeing of the fibers.

Polyglycol ethers containing basic nitrogen are particularly valuable in the process according to the invention, for example, polyglycol ethers of aliphatic, particularly higher alkylated or acylated diand polyamines, whereby one long or several shorter polyglycol ether chains can be bound by way of the nitrogen, such as ethylene oxide condensation products of higher monoalkylor alkenylethylene-diamine, -diethylenetriamine, -triethylenetetramine or of lauroyl-, myristoyl-, oleoyl-, palmitoyl-, stearylaminoethylamine, -ethylenediamine, -diethylenetriamine. Depending on the type and composition of the lipophilic component of these compounds, the number of alkyleneoxy, especially ethyleneoxy groups in these polyglycol ethers is, in all, at least 4, preferably more than 8 to about 100 ethyleneoxy radicals. They can be arranged in one single or in different chains and, to strengthen the lipophilic character, also single ethyleneoxy groups can be alkyl-substituted (particularly methyl-substituted) or phenyl-substituted.

The number of alkyleneoxy groups in these polyglycol ethers should ensure hydrophilic properties and should be so great that the compounds are, at least, easily dispersible in water and, preferably are soluble therein. The use of mixtures of these substances with low to high contents of ethyleneoxy groups is often advantageous and leads to better dispersions. Examples of polyglycol ethers containing lipophilic groups which are usuable according to the invention are: stearyl-diethylenetriamine polyglycol ethers with 17 ethyleneoxy groups, addition product of 2 mols of styrene oxide and 50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine, nonylphenol polyglycol ethers with 5 ethyleneoxy groups, coconut oil fatty acid di-fl-hydroxyethylamide polyglycol ethers with 15-17 ethyleneoxy groups, octylphenoxyacetic acid polyglycol ethers with 3-5 ethyleneoxy groups, addition product of 2 mols of 1,2-propylene oxide and 50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine, oleylamine polyglycol ethers with 7 ethyleneoxy groups, stearoyldiethylenetriamine polyglycol ethers with 17 ethyleneoxy groups, octylphenol polyglycol ethers with 4 ethyleneoxy groups and higher fatty acid, acid-B-amino-lower alkyl ester polyglycol ethers with 3 ethyleneoxy groups.

It is particularly advantageous if the impregnating liquor also contains amides in addition to the fatty acid salts and the polyglycol ethers.

The amides usable according to the invention are derived from the higher fatty acids mentioned above in connection with the salts and from monohydroxyalkylamines, e.g. from fi-hydroxyethylamine, 'y-hydroxypropylamine or [3, -dihydroxypropylamine, from bis-(w-hydroxyalkyl)-amines such as bis-(fi-hydroxyethyD-amine or bis-('y-hydroxypropyl -amine or bis-(ot-methyl-fi-hydroxyethyl)-amine or N-alkyl-N(w-hydroxyalkyl)-amines such as N-methylor N-ethyl- N-(B-hydroxyethyD-amine or N-methylor N-ethyl-(y-hydroxypropyl)-amine.

The bis-(w-hydroxyalkyl)-amides are preferred, particularly those the hydroxyalkyl radicals of which contain two or three carbon atoms such as bis-(fl-hydroxyethyU- amides or bis-('y-hydroxypropyD-amides of coconut oil fatty acids.

A preferred mode of carrying out the first aspect of the invention in practice comprises especially in the dyeing of acrylic slubbings, but also of the other acrylic fiber materials mentioned hereinbefore:

Mixing a cationic (basic) dyestuff with a water-soluble strong organic acid, preferably, acetic acid of a content of from about 60% of CH COOH, in the case of aqueous dilute acetic acid, up to pure glacial acetic acid and diluting the dyestuff-acid mixture with hot water to a concentration of from to 350 grams (g.), and preferably from to 60 g. of glacial acetic acid (CH COOH) per 1000 g. of final impregnation liquor, the amount of dyestuff corresponding to saturation of the final liquor therewith at a temperature of 40 to 60 C. in those cases where deep shades are desired;

Adding to the resulting mixture, as a dyestuif migration controlling dye assistant one of the following compositions:

(I) A dye assistant composition consisting of:

(a) a water-soluble salt of a saturated aliphatic monocarboxylic acid of from 8 to 14 carbon atoms, the cation of which is selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxy-lower alkyl-substituted ammonium ion and hydroxy-lower alkyl-substituted ethylene-diammonium ion; and

(5) A polyglycol ether obtained by condensing:

(1) A compound selected from the class consisting of (i) a fatty, preferably saturated alcohol of from 8 to 20 carbon atoms,

(ii) a fatty, preferably saturated acid of from 8 to 20 carbon atoms,

(iii) an alkyl-substituted phenol wherein alkyl has a total of at least 8, and preferably from 8 to 12 carbon atoms,

(iv) the reaction product of a higher fatty, preferably wholly saturated alcohol of from 8 to 20 carbon atoms and ammonia, or an aliphatic/ amine having from 2 to 4 basic nitrogen groups separated from each other by from 2 to 3 carbon atoms, in a molar ratio of about 1:1,

(v) the amide of a preferably wholly saturated fatty acid of from 8 to 20 carbon atoms amidified with a mono, dior tri-hydroxy-lower alkylsubstituted amine, with, per mol of (1) (2) from 2 to 100 mol, and preferably from 8 to 60 mol of ethylene oxide, from 0 to 2 mol of propylene oxide and from 0 to 2 mol of styrene oxide; or

( 8') a polyglycol ether obtained by condensing:

(vi) an amino-lower alkyl ester of a preferably wholly saturated fatty acid of 8 to 14 carbon atoms, with, per mol thereof,

(2') from 2 to 10 mols of ethylene oxide: or

(I') a dye assistant composition consisting of:

('y) an amide of (a) a preferably wholly saturated aliphatic carboxyiic acid of from 8 to 20, and preferably 8 to 14 carbon atoms, or

(b) an alkyl phenoxy-substituted lower alkanoic acid wherein the alkyl substituent has from 8 to 12 carbon atoms,

amidified with a member selected from the group consisting of mono-, diand tri-hydroxy-lower alkyl amines and the lower alkyl ethers thereof; and

(,8) a polyglycol ether which is the condensation product of a member selected from the group consisting of a saturated fatty alcohol of from 8 to 14 carbon atoms and a saturated aliphatic monocarboxylic acid of from 8 to 14 carbon atoms, with from 5 to 30 mols of ethylene oxide per mol of said member; which dye assistant composition is added in an amount of at least about 10 grams and preferably from 10 to grams per liter of said impregnation liquor,

as well as an acid-medium-compatible thickener in sufficient amount to impart to the resulting impregnation liquor a viscosity of at least about 30 centipoises;

(A) Impregnating acrylic fiber material with the aforesaid impregnation liquor,

(B) Removing excess liquor from the impregnated acrylic fiber material to leave on every 100 parts by weight of the said material from about 80 to parts by weight of liquor;

(C) Steaming the resulting impregnated material with saturated steam for about 15 to 30 minutes, and

(D) Rinsing the steamed material with water and drying the same.

Optimal all-round results are obtained when, in lieu of the binary dye assistant compositions defined above, there are used ternary compositions (1") which consist of (a) A water soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkylsubstituted ammonium ion, hydroxyl-loWer-substituted ammonium ion,

(5) A polyglycolether which is obtained (1) as condensation product from a member selected from the group consisting of a saturated fatty alcohol of from 8 to 14 carbon atoms and a saturated fatty acid of from 8 to 14 carbon atoms, and per mol of said member, 4 to 12 equivalents of ethylene oxide, or

(ii) or as condensation product from the reaction product of a higher fatty alcohol of from 8 to 20 carbon atoms and an aliphatic polyamine having at least 2 and not more than 4 basic nitrogen groups separated from each other by from 2 to 3 carbon atoms, in a molar ratio of about 1:1, with, per mol of said reaction product, from 10 to 60 mol of ethylene oxide, 0 to 2 mol of propylene oxide and 0 to 2 mol of styrene oxide,

and

(7) An amide of a saturated aliphatic mono-carboxylic acid having from 8 to 14 carbon atoms amidified by a member selected from the group consisting of monoand di-hydroxy-lower alkyl-amines and lower alkyl ethers thereof, the weight ratio of (a) to the sum of (,8) and (7) being smaller than 3:1, and preferably in the range of 2:1

Highest color yields are obtained with those of the ternary dye assistant compositions defined above in which component ([3) is a condensation product as defined under (i), supra.

The ratio of fivy is not critical.

In lieu of the dye assistants enumerated above, it is also possible to use a polyglycol ether defined as component (B) or (fl) of dye assistant composition (1), su ra, alone, but this leads to undesirable foam formation during padding and also imparts to the dyed tow a. less lofty, drier handle and can affect detrimentally the running properties of the dyed material, especially in the Turbo stapler.

That the use of the substantially non-ionogenic or mixed non-ionogenic/anionic dye assistants in the process according to the invention prevents the formation of the undesirable sandwich eifect and favorably controls the migration of the dyestuif during steaming is especially unexpected, for anionic dye assistants alone, as they have been used in the dyeing of polyacrylonitrile fibers in the batch process, and especially water-soluble salts of saturated fatty acids of 8 to 14 carbon atoms of the type mentioned above, when used as the exclusive dye assistant in the process according to the invention, lead to uneven dyeings in particular in the case of the preferred compound dyeing, i.e. dyeing with dyestutf mixtures, in which case the last-mentioned anionic agents lead to dyeing in ununiform shades of the various dyestuffs in the mixed dyes.

Furthermore, it is particularly suprising that better dyestuff yields with equally good or even better fastness properties are achieved in the process according to the invention with the above-listed dye assistants on acrylic fiber materials in a stronger acid medium than had hitherto been recommended; for it would have been expected that a stronger acid medium would decrease the dissociation of the basic dyestuffs, especially the more conventionally preferred ones yielding, in aqueous solution, a pH in the range of 3 to 5, and would also decrease the dissociation of the dyestuff-afiinic groupings in the acrylic fiber molecules, and would thus increase the tendency of the dyestuff to remain in the dye liquor and decreas the receptivity of the acrylic fibers for the dyestuff.

However, contrary to that expectation, when using the above-listed dye-assistants in a pad liquor of the above-defined pH range, of about 2 to 4, and preferably about 2.5 to 3.5 the receptivity of the acrylic fibers, especially of acrylic tows or tops, is markedly improved, as compared with the various known pad-steaming methods at pH ranges between 4.5 and 7 and higher, mentioned above.

A further unexpected advantage of the process according to the invention resides in the fact that the resulting dyed tows or tops possess a substantially loftier, more voluminous, fuller handle than those obtained under otherwise identical conditions with a pad liquor of a pH above 4.5 which contains the hitherto used dye assistants.

As salts of suitable saturated aliphatic monoearboxylic acids, the dye assistants used in the impregnating liquors according to the first aspect of the invention contain, for example, alkali metal salts such as lithium, sodium or potassium salts, ammonium or N-substituted ammonium salts of caprylic, pelargonic capric, lauric or myristic acid or the mixtures of acids comprised by the generic term coconut oil fatty acids, or of decyloxyacetic acid, lauryloxy acetic acid, decylthioacetic acid or lauryl thioacetic acid. N-substituted ammonium salts contain as substituent or substituents of the amino nitrogen atom, in particular, lower alkyl such as the methyl or ethyl group, hydroxy-lower alkyl groups such as the fi-hydroxyethyl or 'y-hydroxypropyl group, or lower alkoxy-lower alkyl such as the B-methoxyethyl or ,B-ethoxyethyl or 'y-methoxyp-ropyl or 'y-ethoxypropyl group. Two of these N-substituents together with the amino nitrogen atom can also form a ring, in particular, the piperidine or morpholine ring.

The alkali metal, the lower alkyl ammonium or hydroxy-lower alkyl ammonium salts, chiefly the monoand bis-(fl-hydroxyethyl)-ammonium or monoand bis-(yhydroxypropyl)-ammonium, the N-methyl-N-(fi-hydroxyethyl) -ammonium, N-methyl-N,N-bisfi-hydroxyethyl ammonium or N-methyl-N-(l3,'y-dihydroxypropyl)-amm'onium salts of coconut oil fatty acids have proved to give particularly satisfactory results as components in the dye assistant mixture defined under (I), supra.

The acid reaction of the impregnating liquor is brought about by the addition of adequate amounts of fatty acid; most advantageously the impregnation liquor contains the above-given amounts of acetic acid. The pH of the impregnation liquor is then between 2 and 4.5, and preferably adjusted to 2.5 to 3.5.

Polyglycol ethers particularly suitable for use as dye assistants in the process according to the invention, either alone or, preferably, in mixture with other components as defined above under (I), (I') and (1"), are the reaction products of 4 to 30, preferably 8 to equivalents of ethylene oxide, with 1 equivalent of octyl, decyl, dodecyl or tetradecyl alcohol, or with the fatty alcohol mixture comprised by the term coconut oil fatty alcohol or with 1 equivalent of a fatty acid, e.g. one of the fatty acids mentioned above, in particular coconut oil fatty acid.

Amides which are usable in the dye assistants according to the invention are obtained, for example, from the higher fatty acids discussed above by amidification with monohydroxy-lower alkylamines, e.g. fi-hydroxyethylamine, 'y-hydroxypropylamine or B -dihydroxypropylamine, or bis-(hydroxy-lower alkyl)-amines such as bis- (fl-hydroxyethyU-amine or bis-(y-hydroxypropyl)-amine or bis- (a-methyl-fl-hydroxyethyl)-amine, or N-lower alkyl-N-(hydroxy-lower alkyl)-amines such as N-methylor N-ethyl-N-(B-hydroxyethylamine) or N-methylor N- ethyl-N- ('y-hydroxypropyl) -amine.

The bis-(hydroxy-lower alkyl)-amides are preferred, in particular those the hydroxyalkyl radicals of which contain two or three carbon atoms, especially the bis- (fl-hy'droxyethyl) amides or bis-(y-hydroxypropyhamides o-f conconut oil fatty acids.

The basic dyestuffs usable according to the invention are preferably sulfonic acid group-free dyestuffs of the thiazine, oxazine, diphenylmethane, triphenylmethane, rhodamine, azoor anthraquinone series and, preferably, metliines and azamethines which, in particular, contain onium groups, ammonium groups in particular being regarded as a type of onium group.

Acid medium-compatible thickeners usable in the process according to the invention, are in particular of gum conventional in the textile industry, e.g. so-called crystal gum or thickeners having a cellulose basis such as carob bean flour, tragacanth, British gum, cellulose derivatives such as methyl cellulose or water-soluble salts of carboxymethyl cellulose, or galactomannan. Carob flour thickeners are preferred.

The acrylic fiber materials are impregnated, for example, by printing, coating or spraying, preferably however, by the foulard process.

As has been described above, the impregnating liquor according to the invention is produced advantageously by adding to acetic acid, the basic dyestuif, water, the dye assistant as defined above under (I), (1) and (1") and thickener.

The fibers can be dyed in any form desired, for example in the form of loose fibers, tops, yarn or fabrics, but especially as tops or tow, or rawstock.

Advantageously, the polyacrylonitrile fibers are impregnated with the impregnation liquor at 3050 C. preferably at 4045 C. and then squeezedout to the desired content of impregnating liquor of about to of the weight of the fiber.

The impregnated fiber material is steamed by conventional methods, advantageously with neutral saturated steam.

The padded and steamed goods are advantageously rinsed, preferably with cold or warm water which can contain the additives usual in dyeing, e.g. formic acid or acetic acid and/or substances rendering the goods antistatic, or softeners.

Compared with similar known processes and even compared with the other aspects of this invention, the preferred process mode according to this aspect of the invention for the dyeing of polymeric and copolymeric acrylonitrile fibers has the following advantages; apart from those mentioned hereinbefore:

(l) The impregnating liquor is homogeneous and substantially insensitive to salts and acids, it is therefore stable in the continuous dyeing process;

(2) Even when producing very deep shades, excellent uniformity of the dyeing is attained;

(3) The impregnating liquors are easily produced and can be stored, practically, for an unlimited time;

(4) No undesirable sticking of the liquors to the squeeze rollers occurs;

(5) Color yield and levelness of dyeings, and often also the fixing speed during steaming, are optimal, especially with the above-mentioned amide-component containing ternary compositions.

In lieu of acetic acid, other acids of similar strength can also be used in the process according to the invention, e.g. formic acid or tartaric acid, and also sulfuric acid, provided that the pH of the impregnation liquor ready for use is within the above-stated critical range.

A second aspect of the invention concerns a process for the continuous dyeing, of acrylic fiber materials which is characterized in that the material is impregnated with a preferably thickened, aqueous acid solution of basic dyestuff, with solution contains in amounts of 0.2 to 10% and preferably 0.5 to 5% by weight of the whole liquor, of a dye assistant which consists essentially of a polyglycol ether obtained by condensing (I) a compound selected from the class consisting of (a) a fatty, preferably saturated alcohol of from 8 to 20 carbon atoms, or

(b) a fatty, preferably saturated acid of from 8 to 20 carbon atoms,

() an alkyl-substituted phenol wherein alkyl has a total of at least 8, and preferably from 8 to 12 carbon atoms.

(d) the reaction product of a higher fatty alcohol of from 8 to 20 carbon atoms and an aliphatic polyamine having from 1 to 4, and preferably from 2 to 4 basic nitrogen groups separated from each other by from 2 to 3 carbon atoms, in a molar ratio of about 1:1, or

(e) the amino-lower alkyl ester of a preferably wholly saturated fatty acid of 8 to 14 carbon atoms,

(f) the amide of a preferably wholly saturated fatty acid of from 8 to 20 carbon atoms amidified with a mono-, dior tri-hydroxy-lower alkyl-substituted amine,

mixtures of two or more of said members (a) to (f) with, per mol of (I),

(II) From 4 to 100 mol, and preferably from 8 to 60 mol of ethylene oxide, from 0 to 2 mol of propylene oxide and from 0 to 2 mol of styrene oxide, each of (a), (b) and (c) being preferably condensed with to 12, and each of (d), (e) and (f) with 4 to 20 mols of ethylene oxide alone, per mol of compound (I); or mixtures of such condensation products, and the pH of the solution is adjusted to a value below 4.5 and preferably to a value in the range of 2.5 to 4.0, by adding adequate amount of water soluble, strong organic carboxylic acid, the impregnation being performed at temperatures below the drawing temperature of the dyestuffs, and the treated goods are then subjected to a moist heat treatment by conventional methods.

It is particularly surprising that, for instance, polyglycol ethers such as are obtained by condensation of compounds of type (f), supra, with ethylene oxide, which polyglycol ethers are well known as retarding agents in the exhaustion dyeing of polyamide such as wool, act as dyeing assistant in the pad-dyeing of acrylic fiber materials which actually help to bring about high color yields in a shorter time and complete fixing of such high yield by short-time steaming, especially with slightly superheated steam.

The conditions of treatment set forth under the first aspect of the invention apply equally to this second aspect.

Very deep shades free from sandwich effects are obtained by the continuous dyeing process according to the invention, on polymeric and copolymeric acrylonitrile fibers. The dyeings are distinguished by excellent evenness. In particular, in the preferred continuous dyeing with a mixture of different basic dyestuffs, no spots occur on the fibers which are selectively dyed.

The polymeric and copolymeric acrylonitrile fibers which can be dyed according to this second aspect of the invention are acid-modified polymer fibers and contain at least 80% acrylonitrile, as defined above; they should be fabrics, preferably in the form of woven or piece goods such as plush.

Fabrics are preferred because liquors according to this aspect of the invention have a tendency to adhere more to the squeeze rollers of the pad mangle and to cause more foam than do the liquors falling under the first aspect of this invention. These drawbacks are more serious when pad-dyeing slubbings, tow or rawstock, but not so much when dyeing fabrics.

As hydrophili-c to water soluble, surface active polyglycol ethers, the dyestuff preparation contains the polyglycol ethers described hereinbefore, and more particularly ethyleneoxy condensation products, into which a few substituted epoxides such as styrene oxide and .propylene oxide can be built, of fatty alcohols, i.e. alkanols and alkenols having 8 to 20 carbon atoms; of fatty acids having 8 to 20 carbon atoms; of alkyl phenols having one or more alkyl substituents which together contain at least 8 carbon atoms; of primary or secondary monoor polybasic aliphatic and cycloaliphtaic amines containing at least one higher alkyl or alkenyl radical having at least 8 carbon atoms, or of such alkanolamines having lipophilic alkyl and aralkyl radicals; also of alkanolamides, aminoalkylamides and aminoalkyl esters of higher aliphatic carboxylic acids and higher alkylated alkylaryloxv carboxylic acids.

Basic nitrogen-containing polyglycol ethers of aliphatic. particularly higher alkylated or acylated diand polyamines are particularly valuable in the process according to this aspect of the invention, such as the polyglycol ethers of N-monoalkylor N-monoalkenylmonoor -dior -tri or -tetralower alkylene-di-, or -trior -tetraor -pentaamines having at least 16 carbon atoms in the alkyl or alkenyl radical and at least 15 and preferably more than 25 to about ethyleneoxy radicals, of which a few can be C-methylated and/or C-phenyl substituted. Particularly favourable compounds of this type are addition products of 15 to 20 mols of ethylene oxide to an N- monoalkyl diethylenetriamine the alkyl radical of which contains at least 16 carbon atoms, e.g. a stearyl diethylenetriamine, or addition products of l to 3 mols of styrene oxide or propylene oxide and at least 50 mols of ethylene oxide to an N-monoalkyl diethylenetriamine the alkyl radical of which has 16 to 18 carbon atoms.

Another valuable group of polyglycol ethers are de fined are those of alkanols, alkenols and alkyl phenols which contain hydrophobic hydrocarbon radicals of, in all, at least 8 carbon atoms and at least 5 ethyleneoxy radicals. Particularly suitable compounds of this type are addition products of 4 to 20 mols of ethylene oxide to one alkanol having 8 to 18 carbon atoms such as hexadecanol, or to a .mixture of fatty alcohols known by the general term coconut oil fatty alcohol or an alkyl phenol which contains alkyl radicals having, in all, at least 8 carbon atoms e.g. octylphenol or nonyl phenol or ditert. butyl phenol.

Examples of other suitable polyglycol ethers as defined are: acylaminoalkyl monoor poly-amines which contain hydrophobic hydrocarbon radicals of at least 8 carbon atoms and at least 10 ethyleneoxy radicals, preferably more than 25, of which a few can be C-alkyl or C-aryl substituted. Examples of such compounds are addition products of at least 10 mols of ethylene oxide to lauroyl, myristol, oleoyl, palmitoyl or stearoyl amino-ethylamine, -ethylenediamine or -diethylenetriamine.

In a third aspect, this invention relates to yet another process for the continuous dyeing (pad dyeing or printing) of polymeric and copolymeric acrylonitrile fiber materials and especially of acrylic tow, an impregnating liquor suitable for this process as well as, as industrial products, the fibers dyed With the aid of this liquor.

It is known that natural and synthetic polyamide fiber-s, for example wool or nylon, can be dyed by a continuous process if an impregnating liquor is used which, in addition to acid wool dyestuffs, contains as carrier, watersoluble condensation products of 1 equivalent of fatty acids having 8 to 14 carbon atoms or mixtures of such fatty acids and 1 to 3 equivalents of mono, diand/or tri-alkanolamine. Such condensation products have been described in US. Patent No. 2,089,212. Impregnating liquors containing such carriers require conventionally alkaline to neutral pH-values. It was not to be expected that the aforesaid carriers could be used as dye assistants for the dyeing for polymeric and copolymeric acrylonitrile fiber material with basic dyestuffs from an acid medium.

Particularly, it could not have been expected that an improvement of the affinity of basic dyestuffs to acrylonitrile fibers could be attained by working with such auxiliaries in a stronger acid medium. Rather, it was to be expected that in a stronger acid medium there would be less dissociation of the dyestuff so that it would tend to remain in the dye liquor and, in addition the dissociation of the substituent groups having affinity to the dyestuff and hence constituting dyesite in the fiber molecules would be retarded so that, again, the amount of dyestuff which the fibers could take up would be reduced. We have found, however, that just the opposite happens and that, when dyeing is performed in relatively strong acid medium, i.e. at pH values of about 3.5 to 4 and below, basic dyestuffs are considerably better taken up by acrylonitrile tow than when dyeing is performed in a weakly acid medium, i.e. at pH values of about 5 to 7 or higher.

Another surprising advantage of the process according to the invention is that the products attained, in particular polyacrylonitrile tow, are distinguished by a considerably more voluminous, full handle, whereas products produced by known processes have a fiat handle of unsatisfactory volume.

Experience has shown that when tow has a voluminous handle, it can be better spun and has better spinning properties on stapling (cutting) the tow, for example, in a turbostapler. In addition, a voluminous handle of the products produced according to the invention is decisive for their further use for the production of high bulk yarns used, mainly, for the manufacture of pullovers and similar textile articles. The spotty, shiny appearance of the tow produced by known processes is undesirable for the manufacture of such articles.

Contrary to expectation, it has now been found that polymeric and copolymeric acrylonitrile can be dyed, particularly continuously, surprisingly well and in deep shades by impregnating this material with a thickened aqueous acid impregnating liquor, the acid reaction of which impregnating liquor is due mainly to the presence of low fatty acids, in particular of acetic acid, which is added in amounts of 30 to 300 grams g.) and preferably of 40 to 60 g. of CH COOH (100%) per liter of the impregnation liquor, to attain a pH-value of the liquor below 4.5, preferably between 2.5 and 4.0, and which impregnating liquor contains basic dyestuff, acid-mediumcompatible thickener, and, as dyeing control agent, watersoluble condensation product of 1 equivalent of fatty acids having 8 to 14 carbon atoms or of mixtures of such fatty acids, condensed with l to 3 equivalents of diand/or tri-alkanolamine, as well as, optionally, other auxiliaries conventional in pad dyeing, the impregnation being performed at a temperature below the drawing temperature of these dyestuffs, and steaming the treated goods by conventional methods.

The total amount of the condensation product per liter of the impregnation liquor ranges from 15 to 100 g. and, preferably, from to 40 g.

The fatty acid diand/or tri-alkanolamine condensation products used in the impregnating liquor according to this aspect of the invention can be produced by the process described in the US. Patent No. 2,089,212 already mentioned, namely, by heating 1 equivalent of fatty acids with 1 to 3 equivalents of diand/or trilower alkanolamines, particularly di or tri-ethanolamine While splitting off more than 1 mol of water. The commercial mixtures known as coconut oil fatty acids are chiefly used as fatty acids for this purpose. They consist mainly of lauric acid and, in addition, contain varying amounts of the fatty acids having 8, 10 and 14 carbon atoms. Although diethanolamine in a molar ratio of 2 mols is preferred, it can be wholly or partially replaced by other lower alkanolamines, eg by triethanolamine, di-2- propanol-amine or di-3-propanolamine. In particular, on using tri-alkanolamines and fatty acids having 8 to 12 carbon atoms, a satisfactory dispersability of the condensation product in the dye liquor is achieved even when using in the condensation of the said product a molecular ratio of 1:1 and splitting off only one mol of water. Generally, however, it is of advantage if a multiple of the stoichiometrical amount, preferably twice the amount, of alkanolamine is used in the condensation reaction. It is also favorable when at least one mol of the alkanolamine used contains hydrogen bound to the nitrogen atom so that acid amide formation is possible.

The basic dyestuffs used according to the invention are advantageously of the following classes of dyestuffs: thiazines, oxazines, diphenyl methanes, triphenyl methanes, rhodamines, azo or anthraquinone dyestuffs which, in particular, contain onium groups, and, preferably, methines and azamethines; ammonium groups in particular being regarded as onium groups.

Examples of thicknes which are compatible with an acid medium are the soluble types of gum usual in the textile industry, e.g. so-called crystal gum or thickeners based on cellulose such as locust bean flour, tragacanth, British gum, polysacharides or cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose. Locust bean flour thickneners are preferred. Galactomannan may also be used.

The padding liquor can contain as other auxiliaries usual in the textile industry, for example organic solvents such as ethyleneglycol monoethylether or thiodiethylene glycol, as well as ethylene cyclic carbonate.

As polymeric and copolymeric acrylonitrile fibers, particularly those are meant the greater portion of which, preferably to practically consists of this material which possess an adequate number of dyesites.

The acrylic fibers are impregnated, for example, by printing, coating or spraying, preferably, however, by padding.

The impregnating liquor according to the invention is advantageously produced by pasting the basic dyestuff with the above-defined amount of acetic acid, preferably 60 to 80%-acetic acid, adding to the mixture hot water and an aqueous solution of the condensation products as defined, and, optionally, other auxiliaries usual in dyeing and thickener.

The acrylic fibers can be dyed according to the invention in the form desired, for example, in the form of flocks, yarn and fabrics, and especially in the form of tow, top or rawstock.

The polyacrylonitrile fibers are advantageously impregnated at 30-40" C. and then freed from excess of impregnating liquor to leave on the fibers only a content of impregnating liquor of about 60 to calculated on the dry weight of the fibers.

The impregnated fibers are steamed by conventional methods, advantageously with neutral saturated steam, without intermediate drying.

The dyed and steamed goods are advantageously rinsed, preferably with cold or warm water which can contain the additives usual in dyeing, e.g. formic acid or acetic acid or also substances which make the goods antistatic, or softeners.

By following the process according to the invention, dyeings on polymeric and copolymeric acrylonitrile fibers of very deep shades are obtained, which are distinguished by their excellent uniformity.

Particularly when using a mixture of different basic dyestuffs, as is preferred in continuous dyeing, the undesirable selective dyeing of the different dyestufi components of the mixture is avoided and fiber material dyed in perfectly level deep shades is obtained.

When compared with the impregnation liquors of the first aspect of the invention, and especially the preferred mode of carrying the latter out in practice, the liquors of this third aspect are somewhat less stable at higher temperatures (above 50) and may show a tendency to form separate layers. Also they tend to greater formation of foam.

The follOWing non-limitative examples serve to illustrate the several aspects of the invention. The temperatures are given therein in degrees centigrade. Where not otherwise expressly stated, parts and percentages are given by weight. The relationship of parts by weight to parts by volume is as that of grams (g.) to milliliters (ml.).

Example 1 19.2 g. of the red dyestuff of the formula I ICH3 bill /C2H5 6.2 g. of the yellow dyestuff of the formula are pasted with 80 ml. of cold 60% acetic acid, and 200 ml. of hot water are added thereto.

40 g. of a dye assistant composition consisting of 35 parts of N-methyl-N,N-bis-(fi-hydroxyethyl)-ammonium salt of coconut oil fatty acid, 35 parts of dodecyl alcohol pentaglycol ether and 30 parts of coconut oil fatty acid N,N-bis-(fl-hydroxyethyD-amide, as Well as 100 ml. of a galactomannan thickener prepared by pasting 4 g. of galactomannan with 20 ml. of ethanol and adding thereto 200 ml. of hot water, are admixed with the dye paste, the Whole is made up to 1 liter with water and the impregnation liquor thus prepared is brought to a temperature of 30-40". The pH of this liquor is about 3.5-4.

Polyacrylonitrile tow, the fibers of which have a polymerization number of about 35,000 and possess about 46 millimols of sulfonic acid groups and 17 millimols of carboxyl groups as dyesites, per 100 g. of fibers, is impregnated with this liquor, the fibers are squeezed off to a liquor content of 110%, calculated on the dry weight of the fibers, and steamed for 20 minutes with saturated steam at 102 under slight excess pressure.

The dyed goods are then rinsed several times with 45 warm water and treated with an aqueous solution containing 4 g. per liter of an antistatic and 2 g. per liter of a fabric softener.

Excellently level, deep bluish red fibers are obtained.

Even better results are obtained when fixing the dye in the padded fiber materials in this and the following examples with slightly superheated steam of about 103-104", in lieu of saturated steam.

Coconut oil fatty acid N,N-bis-(,B-hydroxyethyl)-amide is produced by condensing coconut oil fatty acid methyl TABLE 1 Example Dye assistant composition Number 2 35 parts of sodium or potassium salt of coconut oil fatty acid; 35 parts of tetradecyl alcohol decaglycol ether; 30 parts of lauric acid N,N-bis-(B-hydroxycthyD-amide.

3- 35 parts of bis-(B-hydroxyethyD-ammonium salt of lauric acid; 35 parts of dodecyl alcohol pentaglycol ether; 30 parts of coconut oil fatty acid N ,N-bis-(fl-hydroxyethyl)- amt e.

4 35 parts of ammonium salt of coconut oil fatty acid; 30 parts of the condensation product of palmitic acid and ethylene oxide in a molar ratio of 1:7; 35 parts of lauric acid monoethanol amide.

5 1 part of N-methyl-N,N-bis-(B-hydroxyethyl)ammonium salt of laurie or myristic acid; 3 parts of addition product of 2 mols of styrene oxide and 50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenctriamine; 1 part of laurcilc acid or myristic acid N,N-bis-(;8 hydroxyethyl)- ami e.

6 1 part of N-methylN,N-bis-(6,y-dihydroxyoropyl)-am monium salt of coconut oil fatty acid; 1 part of stearyldiethylenetriamine polyglycol ether having 17 ethyleneoxy groups; 1 part of coconut oil fatty acid N ,N-bis- (B hydroxyethyD-amide.

7 1 part of sodium or potassium salt of cocoaut oil fatty acid; 1 part of addition product of 2 mols of styrene oxide and 50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine; 1 part of lauric or myristic acid N ,N-bis- (fl hydroxyethyl)-amide.

8 35 parts of bis-(B-hydroxyethyD-ammonium salt of lauric acid; 35 parts of stearyl-diethylenetriamine polyglycol ether having 11 ethyleneoxy groups; 30 parts of coconut oil fatty acid N,N-bis-(B-hydroxyethyD-amide.

Example 9 20 g. of the yellow dyestuff used in Example 1 are pasted in g. of 80% acetic acid in the cold and dissolved with 600 ml. of hot Water. 4 g. of galcatomannan as acid resistant thickener are slurried with 30 ml. of ethanol and mixed with cold water and this mixture is added to the above solution while stirring. 30 g. of a mixture of 1 part of coconut oil fatty acid bis-(B-hydroxethyl)-ammonium salt, 1 part of an addition product of 2 mols of styrene oxide and about 55 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine and 1 part of coconut oil fatty acid N,N-bis-(,B-hydroxethyD-amide are then added, the whole is brought up to one liter with water and the finished impregnating liquor is brought to 30-40. The pH of this liquor is about 3 to 4.

Polyacrylonitrile tow, having a polymerization degree of about 35,000 and about 154 millimols carboxyl dyesites, per g. of fibers, is impregnated with its liquor and the material is further treated as given in Example 1.

Excellently level yellow colored material is obtained.

Similar results are obtained with the same procedure if 10 g. of a mixture of 1 part of the salt mentioned above, 2 parts of the stearyl-diethylenetriamine polyglycol ether mentioned above and 1 part of coconut oil fatty acid bis- (B-hydroxyethyD-amide are used.

If, instead of the dystufif given, 33.5 g. of a mixture of dyestuffs consisting of 27 g. of the dyestulf of the CH3 5H.

CHaO

1 5 3 .5 g. of the dyestuff of the formula and 3.0 g. of the dyestuff of the formula are used and otherwise the procedure given in Example 9 is followed, then excellently level navy blue colored fibers are obtained.

Example 10 g. of the dyestuff of the formula are slurried in 60 g. of 80% acetic acid in the cold and dissolved with 600 ml. of hot water. 4 g. of galactomannan are slurried with 2 0 ml. of ethanol and mixed with cold water and this mixture is added to the above solution while stirring. g. of a mixture of 1 part of N- methyl-N-(B-hydroxyethyl) -ammonium salt of coconut oil fatty acid, 1 part of stearyl-diethylenetriamine polyglycol ether having 17 ethyleneoxy groups and 1 part of coconut oil fatty acid N,N-bis-(B-hydroxyethyD-amide are then added, the whole is made up to one liter with water and the finished impregnating liquor is heated to 3040". The pH of this liquor is about 3 to 4.

Polyacrylonitrile tow or slubbing of the type used in the preceding examples is impregnated with this liquor and the material is further treated as given in Example 1.

Excellently level red colored material is obtained.

Example 11 10 g. of the yellow dyestuff used in Example 1, 5 g. of the red dyestuff used in Example 1 and -8 g. of the blue dyestuif used in Example 1 are pasted with 30 g. of cold aqueous 85% formic acid solution, and 200 ml. of hot water are added thereto.

g. of the dye assistant composition used in Example 1 as well as 100 ml. of aqueous 2.5% carob bean flour thickener solution are admixed with the dye paste, the Whole is made up to 1 liter and the impregnation liquor is heated to a temperature of 30-40". The pH of this liqnor is about 2.8.

Polyacrylonitrile tow is impregnated with this liquor, the fibers are squeezed off to a liquor content of 110% and steamed for 20 minutes with saturated steam at 101 under slight excess pressure.

The dyed goods are then rinsed several times with warm water and treated with a solution containing 4 g. per liter of an antistatic and 2 g. per liter of a fabric softener.

Excellently level, deep bluish red fibers are obtained.

Similar results are obtained when using in the above procedure in lieu of formic acid, 40 g. of crystalline tartaric acid mixed with 40 ml. of water for making up the dyestuff paste.

The pH of the impregnation liquor ready for use is then 3.2.

By using as the acidifying agent in the above example sulfuric acid in an amount of 4% H 80 per liter of impregnation liquor, whereby the pH of the latter is 2.1, similar good results are obtained.

16 Similar results, but, depending on the type of fiber and dyestuff, affording slightly inferior color yields, are obtained if the mixture mentioned in Example 1, of fatty acid ammonium salt, polyglycol ether and fatty acid amide is replaced by an equal amount of one of the dye assistant compositions given below:

TABLE II Example Number 12 1 part of bis-(,d-hydroxyethyl)ammonium salt of coconut oil fatty acid; 1 part of stearyl-diethylcnetriaminc polyglycol other having 17 cthylencoxy groups.

13 1 part of sodium or potassium salt of coconut oil fatty acid, 2 parts of addition product of 2 mols of styrene oxide and -60 mols of ethylene oxide to 1 mol of stearyl-diethyl enetriamine.

14 1 part of N-methyl-N -(B-hydroxycthy1)ammonium salt of lauric acid; 1 part of nonylphcnyl-pentaglycol other.

15 1 part of tris-(B-hydroxyethyl)-ammonium salt of coconut oil fatty acid; 2 parts of stearyl-diethylenetriarnine polyglycol ether having 17 ethyleneoxy groups.

16 1 part of bis-(dhydroxycthyl)-ammonium salt of coconut oil fatty acid; 1 part of coconut oil fatty acid-di-(fi-hydroxyethyl)-amide polyglycol ether having 15-17 ethyleneoxy groups.

17 1 part of dimathyl ammonium salt of coconut oil fatty acid; 1 part of octylphcnoxyacetic acid polyglycol ethcr having 3-5 et-hylcncoxy groups.

18 1 part of morpholininm or pyridinium salt of coconut oil fatty acid; 1 part of addition product of 2 mols of 1,2- propylene oxide and 50 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine.

l9 1 part of bis-(B-hydroxyethyl)-ammoniuru salt of lauric acid; 1 part of addition product of 2 mols of styrene oxide and 50-60 mols of ethylene oxide to 1 mol of stearyldiethylenetriamine.

21 1 part of N-methytN-(ti-hydroxyethyl)ammonium salt of coconut oil fatty acid; 1 part of oleylaminc polyglycol ether having 7 ethylencoxy groups.

22 1 part of N-methyl-N-(dhydroxyethyl)ammonium salt of coconut oil fatty acid; 1 part of addition product of 1 mol of styrene oxide and 50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine.

23 1 part of bis-(dhydroxyethyl)ammonium salt of lauric acid; 1 part. of coconut oil fatty acid B-arninocthylester polyglycol ether having 8 ethyleneoxy groups.

24 1 part of bis-(ti-hydroxycthyl)-ammoniurn salt of pclargonic acid; 1 part of stearoyl-dicthylenetriamine polyglycol ether having 17 ethylcneoxy groups.

25 1 part of ethyl ammonium salt of coconut oil fatty acid; 1 part of addition product of 2 mols of styrene oxide and 50-60 mols of ethylene oxide to 1 mol of stcaryl-dietliylenetriamine.

26 1 part of sodium or potassium salt of coconut oil fatty acid;

1 part of octylphenol polyglycol ether having 7 ethyloneoxy groups.

27 1 part of his-(fl-hydroxyethyl)-ammonium salt of coconut oil fatty acid; 1 part of dodecyl alcohol pentaglycol ether.

28 1 part of sodium or potassium saltof coconut oil fatty acid;

1 part of decyl alcohol hexaglycol ether.

part of Nanethyl-N-(B-hydroxyethyl) ammonium salt of lauric acid; 1 part of tetradecyl alcohol hexaglycol other.

30 1 part of tris-(dhydroxyethyl)-ammonium salt of coconut oil fatty acid; 1 part of dodecyl alcohol pentaglycol ether.

of N-methyl-N,N-bis-(fl-hydroxycthyl)-ammonium part of dodecyl alcohol pentaglycol 31 2 parts salt of myristic acid; 1 ether.

32 1 part of dimethyl-ammonium salt of coconut oil fatty acid; 1 part of dodccyl alcohol pentaglycol ether.

33 1 part of morpholine salt of coconut oil fatty acid; 1 part of dodecyl alcohol pentaglycol ether.

34 1 part of bis-(B-hydroxyethyl)ammonium salt of lauric acid; 1 part of dodecyl alcohol pentaglycol ether.

35 1 part of bis-(fl-hydroxyethyl)ammonium salt of coconut oil fatty acid; 1 part of dodecyl alcohol decaglycol ether.

36 1 part of N-methyl-N-(B-hydroxyethyl)ammonium salt of coconut oil fatty acid; 1 part of tetradecyl alcohol hcxaglycol ether.

TABLE II-Continued Example Number 37- 1 part of N-Inethyl-N-(B-hydroxyethyl)ammonium salt of coconut oil fatty acid; 1 part of tetradccyl alcohol heptaglycol ether.

38 1 part of bis(oz-methyl-fl-liydroxyethyl)ammonium salt of coconut oil fatty acid; 1 part of dodecyl alcohol pentaglycol ether.

39 1 part of bis(fl-hydroxyethyl)ammonium salt of coconut oil fatty acid; 1 part of coconut oil fatty acid N,N-bis- (IS-hydroxyethyD-amide.

40 1 part of bis-(Bhydroxyethyl)ammonium salt of pelargonic acid; 1 part of coconut oil fatty acid pentaglycol ether.

41 1 part of ethylammonium salt of coconut oil fatty acid;

1 part of coconut oil fatty alcohol pentaglycol ether.

42 1 part of sodium or potassium salt of coconut oil fatty acid;

1 pat of coconut oil fatty acid N ,N -bis-(B-hydroxyethyl)- arm e.

43 2 parts of N-methyl-N,N-bis-(fi-hydroxyethyD-ammonium salt of lauric acid; 1 part oflauric acid N ,N -bis-(B-hydroxyethyl)-amide.

44 1 part of N-methyl-N,NbiS-(l ,'y-dihydroxypropyD-ammonium salt of coconut oil fatty acid; 1 part of coconut oil fatty acid N,N-bis-(fl-hydroxyethyl)-amide.

By using, with otherwise the same procedure as given in Example 1, instead of the 40 g. of the dye assistant mentioned in that example, 10, 20 or 30 g. of the mixture given in the second column of the following Table HI as dye assistants, and employing the acid given in the third column of said table in the amount stated, dyeings having similar properties are obtained.

TABLE III Ex. No. Dye assistant composition Acid 46 1 part of N-methyl-N,N-bisQG-hydroxyethyl)- 50 g. of glaammonium salt of coco-oil fatty acid; 12 parts cial of the condensation product of stearic acid acetic and ethylene oxide in a molar ratio of 1:7. acid. 47- 1 part of coconut oil fatty acid diethanol- 50 g. of

amide; 1 part of lauryl alcohol hexaglycol tartaric ether. acid. 48- 1 part of octylphenoxy acetic acid N,N-bis-(/3- 50 g. of

hydroxyethyD-amide; 1 part of coconut oil tartaric fatty acid pentaglycol ether. acid.

Example 49 20- g. of the dyestuif of the formula are pasted in 150 g. of 80% acetic acid in the cold and dissolved with 600 ml. of hot water. 4 g. of galactomannan are pasted with 20 ml. of ethanol and mixed with cold water and this mixture is added to the above solution while stirring. 30 g. of a mixture of 1 part of coconut oil fatty acid di-(B-hydroxyethyl)-ammonium salt and 1 part of an addition product of 2 mols of styrene oxide and 5060 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine are then added and the whole is made up to 1 liter with water. The finished impregnating liquor is heated to 3040. The pH of this liquor is about 3-4.

Polyacrylonitrile plush of the same fiber material as the tow dyed in Example 1 is impregnated with this liquor, the material is squeezed out to a liquor content of 100% and the goods are steamed for 20 minutes with saturated steam at 102 under slight excess pressure.

The dyed goods are then rinsed several times with 45 warm water, then treated with a solution which contains 4 g. per liter of antistatic and 2 g. per liter of fabric softener, and dried.

Excellently level yellow-colored material is obtained.

If the mixture of coconut oil fatty acid di-(B-hydroxyethyl)-ammonium salt and an addition product of styrene oxide and ethylene oxide to stearyl-diethylenetriamine given above is used in a Weight ratio of 1:3 instead of 1:1 and otherwise the procedure given in the example is followed, similar results are obtained.

Similar results are also obtained by using 4050 g. of acetic acid, formic acid or tartaric acid instead of 150' g. of 80% acetic acid, with otherwise the same procedure as given in the example.

Similar results are also obtained by using in lieu of 30 g. of the dye assistant composition used in Example 49, only 5, 10 or 20 g. thereof.

Example 50 20 g. of the dyestuff of the formula Cur-0112011 Q C-NN N (5H. N+ ta are slurred in 100 g. of 80% acetice acid in the cold and dissolved with 600 ml. of hot Water. 4 g. of galactomannan thickener are slurried with 20 ml. of ethanol and mixed with cold water and this mixture is added to the above solution while stirring. 30 g. of a mixture of 3 parts of an addition product of 2 mols of styrene oxide and 50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine and 1 part of coconut oil fatty acid di- (li-hydroxyethyl)-ammonium salt are then added, the Whole is made up to one liter with water and the finished impregnating liquor is heated to 30-40. The pH of this solution is about 3-4.

Polyacrylonitrile piece goods are impregnated with this liquor and the goods are further treated as given in Example 49.

Excellently level blue colored material is obtained.

Example 51 20 g. of the same dyestuff as used in Example 50 are slurried in 100 ml. of 80% acetic acid in the cold and dissolved with 600 ml. of hot water. 10 g. of carob bean flour thickener which have been slurried with 20 ml. of ethanol and mixed with cold water are added to this solution while stirring. Then 5 g. of the polyglycol ether obtained by condensing stearyl diethylenetriamine with per mol thereof, about 17 ethyleneoxy groups and 5 g. of coconut oil fatty acid N,N-bis-(fi-hydroxyethyl)amide, are added, the whole is made up to one liter with water and the temperature of the impregnating liquor is brought to 3040-. The pH of this liquor is about 34.

Polyacrylonitrile slubbing is impregnated with this liquor and the impregnated material is treated as described in Example 1.

Excellently level, blue-colored slubbing is obtained.

If, with otherwise the same procedure, instead of the 10 g. of the dye assistant composition given in Example 51, 10, 20 or 30 g. of the products or mixtures given in the following Table IV are used, then dyeings having similar properties are obtained.

oil fatty acid N,N-bis-(B-l1ydroxyethyl)amide.

TABLE 'IV-Conthfiucil Example Number 1 part of octyphenol polyglycol ether having 4 ethylene oxide groups; 1 part of coconut oil fatty acid N,N-bis- If, with otherwise the same procedure, instead of, in all, 30.7 g. of the dyestuff mixture given in Example 1, the dyestuffs or mixtures of dyestufis given in Column II of the following Table V are used in the amounts given,

(fihydmxyethyn'amlde 5 then dyeings of the shades given in Column HI are ob- 56 1 art of coconut oil fatt acid hexagl 'col ether; 1 part of oconut oil fatty acid l LN-bis-(fi-hgdroxyethyh-amide. tamed whlch also have good propertles' TABLE V Ex. No. II III 57 20 grams:

" O Czfis N Blue.

(C2H5)2N N(C2 5)2 0+ 58 20 grams:

i =N B h- Blue. N+ H1 (kHz,

59 20 grams:

- Z Cl I1 Blue. 3H: 3

60 20 grams:

l CH3 00H; 0H=OH-NH -0 OH: Yellowf+ a C 3 61 20 grams:

C=NN=N N02 C Yellow. (311 62 Mixture of 15 grams:

C=N-N=I;I N02 C1 CH and 20 grams I=N --N Q ZnCla Green. I CHzCHzOH 63 Mixture of 27 grams:

D :4 1 omomon C a TABLE V-Continued III grams:

Green.

QNUJEBM or 86 10 grams:

Red.

87 Mixture of parts:

20 parts:

Double zinc chloride of- 10 parts:

/ N l a):

5 parts:

CH; N

and 26 parts of dam-i119 Black.

Example 88 A mixture of 10 of the dyestuif of the formula 5 g. of the dyestufi of the formula and 8 g. of the dyestufi of the formula ZnCla Polyacrylonitrile tow consisting of fibers of polyacrylonitrile having an average molecular weight of about 60,000 to 70,000 and a dyestuif-binding equivalent value of about 55 millimol, consisting essentially of sulfonic acid groups, per 100 grams of fibers is impregnated with this liquor, the fibers are squezed off to a liquor content of 100% and steamed for 20 minutes with superheated steam at 103. The dyed goods are then rinsed several times with 45 warm water and then treated with a solution containing 4 g. per liter of an antistatic and 2 g. per liter of a fabric softener and dried.

Fibers dyed an excellently level, deep red-brown shade are obtained.

Example 89 20 g. of the dyestuif of the formula H(J NCHa N -N=N N(C2H5)2 211C113 are slurried in 60 ml. of 80% acetic acid in the cold and dissolved with 600 ml. of hot water. g. of carob bean flour thickener which has been slurried with 20 ml. of ethanol and mixed with cold water are added while stirring to this solution. Then 10 g. of nonylphenol polyglycol ether containing ethyleneoxy groups are added, the whole is made up to one liter with water and the impregnating liquor is brought to 30-40". The pH of this liquor is about 3-4.

'Polyacrylonitrile slubbing of an acrylic fiber material as used in the preceding example is treated with this are slurried in 150 ml. of 80% acetic acid in the cold and dissolved with 600 ml. of hot water. 4 g. of galactomannan thickener which have been slurried with 20 ml. of ethanol and mixed with cold water are added to this solution while stirring. Then 10 g. of an addition product of 2 mol of styrene oxide and about 55 mols of ethyleneoxide to stearyl diethylenetriamine are added and the procedure described in Example 88 is followed using polyacrylonitrile plush instead of tow.

Level, yellow-colored plush is obtained.

If instead of the dyestuff mentioned, the dyestulf of the formula is used and the procedure given above is followed, then level, green-colored plush is obtained.

It, with otherwise the same procedure, instead of the 10 g. of the dye assistant composition used in Example 90, 10, 15 or 40 g. of the products or mixtures given below are used as carrier, then dyeings having similar properties are obtained.

T LE liquor following the procedure described in Example 88. AB VI -A slubbing dyed a very elven red shade is obtained. fi g Dyefissistant composition Similar results are obtained on using corresponding amounts of formic or tartaric acid instead of acetic acid. 91 Dodecyl 81001101 Pentaglycol ether- 92 Decyl alcohol hexaglycol ether. If instead of the nonylphenol polyglycol ether men- 93 g g l l fi l g fi i t h i I 94 0 ecy 3C0 0 603g YCO e er. tioned, octadecanol polyglycol ether having 3 to 5 ethyl 95" Tetmdecylalcohol heptaglycolether enemy groups or an Oleylamme p y y ether 96 Coconut oil fatty acid pentaglyeol ether. ing 7 ethyleneoxy groups is used then with otherwi 97.. 1 part of the condensation product of coconut oil fatty acid fi-amjno-ethyl ester and, per mol thereof; 10 mols of the same procedure, similar red dyemgs on acrylic fiber ethyilene oxidet; l t r t oi 1 th polyglycol ether rlfbtalned by con ensing s earyie yene riamine wit per mo mammal are obtamed' thereof; 2 mols of styrene oxide and about mols of ethylene oxide. Example 98 The condensation product of nonylphenoxyacetic acid with, per mol thereof, 4 mols of ethylene oxide. 20 g. of the dyestuif of the formula S 50 CHQO N If, instead of the dyestuif given in Example 89, one of 01 those given in the following table is used and otherwise a the procedure given in the example is followed, then excellently level dyed goods are also obtained of the H3 55 shades given in column 3 of the table.

TABLE VII Shade on No. Dyestufi polyacrylom'trlle fibres j 99 Q 2 I H01 Yellow.

CH3 H2N-k NH:

N=N 100 I H01 Do.

(EH30 HzN \N)NH2 TABLE VII-Continued Shade on No. Dyestufi polyacrylonitrile fibres 101 /C=NN=T- N 0 2 01- \1\II CH3 O a 0 CH3 'CCH3 102 CCH=CHNH -0 CH; 01-

f+ CH C--N=N-NN 02 C1 Reddish yellow.

104 Same as Example 81 in Table V Yellow;

omnN-omo o N=N=C- 01- Reddish yellow. HaC- -N H 1-C(CH;)2

T Reddish orange. Q

C-N s LII? CH=CHC- 01- Orange, CH3

HsCC-N H (C 2H5) HN- 'NH(C 1H5) HsC- C/ 0 Ha 108 l 01'' Red.

C O O C 2115 0 (CH3): CHzCHaCl 109 C-CH -CH N\ C1" D0.

N CH3 1 110 Same as in Example 65 in Table V Do.

HO---lfiI-CH3 111 G-N=N-N (C2 s) 2 ZnCla Blueish red.

I? C Ha --G (CH3): /CH CH$C1 112 J-CH=CHN 01; Red violet:

1 CH3 C Ha TABLE VIIContinued Shade on No. Dyestufi polyaerylonltrile fibres 113 Same as in Example 78 in Table V Rde Violet 114 Same as in Example 79 in Table V Do.

- (I) C 2H5 01- Greenlsh blue.

115 (C2H5)2N 0/ (C: 5)z

I Cl C H:

1 H a s C H N 2 s): 0/

/ I ZnClr Reddish blue.

C H: 1 1 C CH:O

/" @T Z 01 B n a lue;

120 F g NH:

0 H38 Or Do. H +/C H2-CH2\ 0 I IH-O OH1CHQN\ /CH:

I 011 -0 Hz 121 Same as in Example 64111 Table V Do.

122 Same as in Example 69 in Table V Do.

3 123 -HS 04 Bluelsh green.

0 H3O 124 -N=N N 0 ZnCla' Blue.

TABLE VII-Continued Shade on No. Dyestufi polyaerylonitrile fibres H--CH3 N+ 13s (CHmN-QN: 01- Orange. III CH CH F HCH3 H w N+ I N CH I err. 137 IF C1- DO.

I Cl

138 N(CHz) -N -CH CHaOSOa" Blue.

CH3 II I O NH;

021150 out 139. -N=N-N 01- D0.

]l' NHz 14o N=N ZnClf Scarlet.

I g CH3 C2H50- 141 N=N@T ZnClr Blue.

I|I CH (3H2 fi CONH2 Example 142 19.2 g. of the red dyestutf of the formula FNLCE 0.11.

6.2 g. of the yellow dyestuff of the formula and 5.3 g. of the blue dyestulf of the formula s CHaO CZHS 21101 CHgCHzOH III CH3 Kreuzlingen, Switzerland), the whole is made up with water to one liter and the ready impregnating liquor is heated to a temperature of 30-40". The pH of this liquor is about 3.5 to 4.

Polyacrylonitrile top, the fibers of which consist of a polyactylonitrile having a polymerization degree of about 35,000 and possessing per 100 g. thereof about 46 millimols of sulfonic acid groups and 17 millimols of carboxyl groups, is impregnated with this liquor, the fibers are squeezed oil to a liquor content of 140% and steamed for 20 minutes with superheated steamat 103 under slight excess pressure.

The dyed goods are then rinsed several times with 45 warm water and treated with a solution which contains 4 g. per liter of an antistatic agent and 2 g. per liter of a fabric softener.

Excellently level, deep bluish-red colored top (slubbing) is obtained.

By using, with otherwise the same procedure, instead of 40 g. of the condensation product given in Example 142, 30 g. of the condensation product of 1 equivalent 'fatty acid, consisting of a mixture of lauric acid and myristic acid (molar ratio 1:1), with 2 equivalents of triethanola-mine, equally deep shades on tows are obtained.

Similar results are also obtained when using in the above example, equal amounts (15 g.) of coconut oil fatty acid diethanolamide and in lieu of acetic acid, 45 g. of 80%-formic acid per liter, or when using 15 g. of lauric acid mono-ethanolarnide and the same amount (80 ml.) of '60%-acetic acid.

If, with otherwise the same procedure as used in Example 142, instead of in all 30.7 g. of the dyestuff mixture given in the example, the dyestuffs or dyestuff mixtures given in Column III of the following Table VI-I-I are used in the amounts given in Column H, then dyeings on polyacrylonitrile fiber of the shades given in Column W which have equally good properties, are obtained.

TABLE VIII Ex. No. II III IV 143 20 grams Same as Example 57 Blue. 144 ..do Same as Example 58. Do.

Same as Example 59-. D0.

Yelllojw 33.5 grams. 150 griamsnn Same as Example 64 B Same as Example 78. Same as Example 79- Same as Example 80- Same as Example 81 1) Same as Example 82- Same as Example 83- Same as Example 84- Yellow Same as Example 85. Green ..do Same as Example 86- Red. do Same as Example 87 Black.

Example 174 g. of the yellow dyestuif of the formula and g. of the blue dyestufl used in Example 142 are dissolved in 150 ml. of cold 80%-acetic acid and 200 ml. of hot water are poured in 10 g. of the condensation prodnet of coconut oil fatty acid and 1.5 equivalents of diethanolamine (according to Example 18 of U.S. Patent No. 2,089,212), dissolved in 200 ml. of hot water, and 200 ml. of 7.5% galactomannan thickener solution are added to this solution and the whole is made up to one liter with cold water. The pH of the liquor is about 2.5 to 3.

Polyacrylonitrile top is impregnated with this liquor at a temperature of 40, the fibers are squeezed out to a liquor content of and then steamed with saturated steam for 15 minutes at 100-102. The dyed goods are then rinsed in a Lisseuse machine with warm water containing an antistatic of a cation active fatty acid imidazoline derivative type (4 g./liter) and then dried.

Excellently level, voluminous top is obtained which is dyed a deep green color.

Example 175 27 g. of the blue dyestuff used in Example 142 are dissolved in ml. of cold 60% acetic acid and 250 ml. of hot water are added. A solution of 8 g. of the condensation product from 1 mol of coconut oil fatty acid and 2 mols of triethanolamine (produced according to Example 12 of U3. Patent No. 2,089,212) in ml. of hot water and 300 ml. of a hot 4% galactomannan thickener solution are added to this solution and the mixture is made up to one liter with water. The pH of the liquor is about 3-3.5. Polyacrylouitrile fabric of acrylic fibers as used in Example 88 is impregnated therewith at a temperature of about 40, squeezed out to a liquor content of about 90% and then the fabric is treated for 25 minutes under slight excess pressure and at a temperature of about 102, with saturated steam in a steamer. The dyed goods are then rinsed several times with an aqueous solution containing 4 g. per liter of an antistatic of a cation active fatty acid imidazoline derivative type, and finally, are dried.

Fabric dyed evenly in a full blue shade is obtained.

Example 176 15 g. of the yellow dyestuii used in Example 174, 7.2 g. of the blue dyestuff of the formula I oo 2)zN CHa CHaOSOa' C I I o o O NIH and 4.8 g. of the blue dyestuff of the formula are pasted with 60 ml. of cold 80%-acetic acid, and 200 ml. of hot water are added thereto.

200 ml. of a 2% galactomannan solution in 100 ml. of hot water as well as 10 g. of a migration-controlling dye assistant consisting of the condensation product of coconut oil fatty acid and 2 equivalents of diethanolamine are added to this solution, the whole is made up to one liter and the impregnation liquor prepared is brought to a temperature of 30-40". The pH of this liquor is about 3.5-4.

Polyacrylonitrile tow is impregnated with this liquor, the fibers are squeezed 01f to a liquor content of 100% and steamed for 20 minutes with saturated steam at 102 under slight excess pressure.

The dyed goods are then rinsed several times with 45 warm water and treated with a solution containing 4 g. per liter of an antistatic agent and 2 g. per liter of a fabric softener.

Excellently level, bright yellowish-green fibers are obtained.

Claims (1)

1. A PROCESS FOR THE CONTINUOUS DYEING OF ACRYLIC FIBER MATERIALS, COMPRISING (A) IMPREGNATING ACRYLIC FIBER MATERIAL HAVING ACID DYESITES WITH THICKENED AQUEOUS ACID LIQUOR OF BASIC DYESTUFF, AT A TEMPERATURE BELOW THE DRAWING TEMPERATURE OF THE DYESTUFF, WHICH LIQUOR CONTAINS (I) A DYE ASSISTANT COMPOSITION CONSISTING ESSENTIALLY OF: (A) A WATER-SOLUBLE SALT OF A SATURATED ALIPHATIC MONOCARBOXYLIC FATTY ACID HAVING 8 TO 14 CARBON ATOMS WITH A MONO- TO DIVALENT CATION SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL ION, AMMONIUM ION, LOWER ALKYL-SUBSTITUTED AMMONIUM ION, HYDROXYLOWER ALKYL-SUBSTITUTED AMMONIUM ION, AND, FOR EVERY 3 PARTS BY WEIGHT OF (A) IN SAID COMPOSITION AT LEAST ONE PART OF A MEMBER SELECTED FROM THE CLASS CONSISTING OF (B) POLYGLYCOLETHER, ($) AMIDE AND (B/$) POLYGLYCOLETHER-AMIDE MIXTURES, SAID POLYGLYCOLETHER (B) BEING OBTAINED AS (I) CONDENSATION PRODUCT OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF A SATURATED FATTY ALCOHOL OF FROM 8 TO 14 CARBON ATOMS AND A SATURATED FATTY ACID OF FROM 8 TO 14 CARBON ATOMS, AND, PER MOL OF SAID MEMBER, 4 TO 12 EQUIVALENTS OF ETHYLENE OXIDE, OR AS (II) CONDENSATION PRODUCT FROM THE REACTION PRODUCT OF A HIGHER FATTY ALCOHOL OF FROM 8 TO 20 CARBON ATOMS AND AN ALIPHATIC POLYAMINE HAVING AT LEAST 2 AND NOT MORE THAN 4 BASIC NITROGEN GROUPS SEPARATED FROM EACH OTHER BY FROM I TO 3 CARBON ATOMS, IN A MOLAR RATIO OF ABOUT 1:1 TO 1:2 AND, PER MOL OF SAID REACTION PRODUCT, FROM 10 TO 60 MOL OF ETHYLENE OXIDE, 0 TO 2 MOL OF PROPYLENE OXIDE AND 0 TO 2 MOL OF STYRENE OXIDE, SAID AMIDE ($) BEING THAT OF A SATURATED ALIPHATIC MONOCARBOXYLIC ACID HAVING FROM 8 TO 14 CARBON ATOMS AMIDIGIED BY A MEMBER SELECTED FROM THE GROUP CONSISTING OF MONO- AND DI-HYDROXY-LOWER ALKYL-AMINES AND LOWER ALKYL ETHERS THEREOF, IN A MOLAR RATIO OF (ACID):(AMINE) OF 1:1 TO ABOUT 1:2, WHICH DYE ASSISTANT COMPOSITION IS ADDED IN AN AMOUNT OF AT LEAST ABOUT 2 GRAMS PER LITER OF SAID IMPREGNATION LIQUOR; (II) ACID-MEDIUM-COMPATIBLE THICKENER IN SUFFICIENT AMOUNT TO IMPART TO THE RESULTING IMPREGNATION LIQUOR A VISCOSITY OF A LEAST ABOUT 30 CENTIPOISES; (III) A WATER-SOLUBLE STRONG ACID IN SUFFICIENT AMOUNT TO IMPART TO SAID LIQUOR A PH UP TO ABOUT 4, (B) REMOVING EXCESS LIQUOR FROM THE IMPREGNATED ACRYLILC FIBER MATERIAL TO LEAVE ON EVERY 100 PARTS BY WEIGHT OF THE SAID MATERIAL AT LEAST ABOUT 80 PARTS BY WEIGHT OF LIQUOR; (C) STEAMING THE RESULTING IMPREGNATED MATERIAL, AND (D) RINSING THE STEAMED MATERIAL AND DRYING THE SAME.